Diimine metal complexes, methods of synthesis, and methods of using in oligomerization and polymerization

ABSTRACT

Methods for making α-diimine metal complexes are described. The methods comprise forming an α-diimine metal complex imine bond in the presence of a metal salt or an α-acylimine metal complex. The method is particularly using for the production of α-diimine metal complexes having two different α-diimine nitrogen groups. The α-diimine metal complexes are useful for polymerizing or oligomerizing olefins.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a Divisional Application of U.S. patent application Ser. No.11/186,039, filed Jul. 21, 2005 and entitled “Diimine Metal Complexes,Methods Of Synthesis, And Methods Of Using In Oligomerization AndPolymerization.” The present application is also related to U.S. Pat.No. 7,129,304 issued Oct. 31, 2006 and U.S. Pat. No. 7,268,096 issuedSep. 11, 2007, each having like title. Each of these patent and patentapplications is hereby incorporated by reference herein in its entirety.

FIELD OF THE INVENTION

The present application relates generally to olefin oligomerization.More particularly, the present application relates to α-diimine metalcomplexes, methods of producing α-diimine metal complexes, and the useof α-diimine metal complexes in the oligomerization and/orpolymerization of olefins.

BACKGROUND OF THE INVENTION

Olefins, also commonly known as alkenes, are important items ofcommerce. Their many applications include employment as intermediates inthe manufacture of detergents, as more environmentally friendlyreplacements where refined oils might otherwise be used, as monomers,and as intermediates for many other types of products. An importantsubset of olefins are olefin oligomers, and one method of making olefinoligomers is via oligomerization of ethylene, which is a catalyticreaction involving various types of catalysts. Examples of catalystsused commercially in polymerization and oligomerization of olefinsinclude alkylaluminum compounds, certain nickel-phosphine complexes, anda titanium halide with a Lewis acid, such as diethyl aluminum chloride.

Another group of olefin polymerization catalysts is derived frompyridine bis-imines. With catalysts of this type, a nitrogen-basedligand engages in a coordination reaction with a transition metal salt.The coordination reaction forms a metal complex, which is a catalystprecursor. The metal complex further reacts with another precursor oractivator to generate a metal alkyl or metal hydride species. Thecatalyst resulting from the generation of the metal alkyl or metalhydride species polymerizes olefins.

Applications and demand for olefin polymers and oligomers continue tomultiply, and competition to supply them correspondingly intensifies.Thus, additional novel and improved catalysts and methods for olefinpolymerization and oligomerization are desirable.

SUMMARY OF THE INVENTION

In an aspect the present invention provides a method for producing anα-diimine metal complex comprising forming at least one imine bond inthe presence of a metal salt, metal complex, or combinations thereof. Inembodiments, the method for producing an α-diimine metal complexcomprises: a) contacting an α-acylimine compound, a metal salt, and aprimary amine; and b) recovering the α-diimine metal complex. In someembodiments, the α-acylimine compound comprises an α-acylimine group andan α-acylimine nitrogen group consisting of an organyl group consistingof inert functional groups or a hydrocarbyl group and the primary aminecomprises an —NH₂ group, a metal salt complexing group and a linkinggroup linking the metal salt complexing group to the —NH₂ group. Inanother embodiment, the α-acylimine compound comprises an α-acyliminegroup and an α-acylimine nitrogen group comprising a metal saltcomplexing group and a linking group linking the metal salt complexinggroup to the α-acylimine nitrogen atom, and the primary amine consistsof an —NH₂ group and an organyl group consisting of an inert functionalgroup or a hydrocarbyl group. In yet another embodiment, the method forproducing an α-diimine metal complex comprises: a) contacting anα-acylimine metal complex and a primary amine; and b) recovering theα-diimine metal complex.

In another aspect, the present invention provides for an α-diimine metalcomplex composition comprising a metal salt complexed to a bidentate ortridentate α-diimine compound wherein the α-diimine compound comprisesan α-diimine group, a first imine nitrogen group, and a second iminenitrogen group which is different from the first imine nitrogen group.In embodiments, the α-diimine compound is tridentate, the α-diiminegroup is derived from an α-diacyl compound, the first imine nitrogengroup consists of a C₁ to C₃₀ organyl group consisting of inertfunctional groups or a C₁ to C₃₀ hydrocarbyl group, and the second iminenitrogen group comprises a metal salt complexing group and a linkinggroup linking the metal salt complexing group to the imine nitrogengroup. In another embodiment, the α-diimine compound is bidentate, theα-diimine group is derived from an α-diacyl compound, the first iminenitrogen group consists of a C₁ to C₃₀ organyl group consisting of inertfunctional groups or a C₁ to C₃₀ hydrocarbyl group, and the second iminenitrogen group consists of a C₁ to C₃₀ organyl group consisting of inertfunctional groups or a C₁ to C₃₀ hydrocarbyl group. In furtherembodiments, the α-diimine metal complex comprises a metal saltcomprising iron complexed to a tridentate α-diimine compoundcomprising: 1) an α-diimine group derived from acenaphthenequinone,phenanthrenequinone, or pyrenequinone; 2) a first imine nitrogen groupconsisting of a 2,6-dimethylphenyl group, a 2,6-diethylphenyl group, a2,6-diisopropylphenyl group, or a 2,6-di-tert-butylphenyl group; and 3)a second imine nitrogen group comprising a metal salt complexing groupand a linking group linking the metal salt complexing group to thesecond imine nitrogen atom.

In yet another aspect, the present invention provides a process forproducing alpha olefins comprising: a) contacting ethylene, an α-diiminemetal complex, and a cocatalyst; and forming an oligomerized ethyleneproduct comprising alpha olefins. In embodiments, the α-diimine metalcomplex comprises a metal salt complexed to an α-diimine compound,wherein the α-diimine compound comprises: 1) an α-diimine group derivedfrom an α-diacyl compound; 2) a first imine nitrogen group consisting ofa C₁ to C₃₀ organyl group consisting of inert functional groups or a C₁to C₃₀ hydrocarbyl group; and 3) a second imine nitrogen groupcomprising a metal salt complexing group and a linking group linking themetal salt complexing group to the imine nitrogen group. In otherembodiments, the α-diimine metal complex comprises a metal saltcomprising iron complexed to an α-diimine compound comprising; 1) anα-diimine group derived from acenaphthenequinone, phenanthrenequinone,or pyrenequinone; 2) a first imine nitrogen group consisting of a2,6-dimethylphenyl group, a 2,6-diethylphenyl group, or a2,6-diisopropylphenyl group; and 3) a second imine nitrogen groupcomprising a metal salt complexing group and a linking group linking themetal salt complexing group to the second imine nitrogen atom.

DESCRIPTION OF THE DRAWINGS

FIG. 1 represents the ORTEP diagram of the X-ray crystal structure forthe α-diimine metal complex produced in Example 5.

FIG. 2 represents the ORTEP diagram of the X-ray crystal structure forthe α-diimine metal complex produced in Example 7.

DETAILED DESCRIPTION OF EMBODIMENTS

The present application discloses α-diimine metal complexes, methods forproducing α-diimine metal complexes, and the use of α-diimine metalcomplexes in the oligomerization and/or polymerization of olefins.

Definitions

For the purpose of this application the designation “α-” represents arelational designation that when preceding a chemical name, eithergeneral or specific, indicates that the two functional groups are onadjacent carbon atoms. Non-limiting examples using the relationalα-designation include, α-dione where the two ketone oxygen atoms arebonded to adjacent carbon atoms, α-diimine where the two imine nitrogenatoms are bonded to adjacent carbon atoms, and α-acylimine where theacyl group oxygen atom and the imine nitrogen atom are bonded toadjacent carbon atoms. The α-relational designation may also be used todescribe other compounds described herein.

For purposes of this application, an “acyl group” is represented by thestructure

wherein the undesignated valences may be hydrogen, an organyl group, ahydrocarbyl group, and/or any other group as indicated herein. Thus, theterm acyl group may include ketones and/or aldehydes. The presentapplication may also refer to substituent(s)/group(s)/atom(s) attachedto the acyl group carbon atom (an acyl carbon group).

For the purpose of this application, the term “imine group” isrepresented by the structure

wherein the undesignated valences can be hydrogen, an organyl group, ahydrocarbyl group, and/or any other group as indicated herein. The termimine group comprises both aldimines and ketimines. The presentapplication may also refer to substituent(s)/group(s)/atom(s) attachedto the imine carbon atom (an imine carbon group) and/orsubstituent(s)/group(s)/atom(s) attached to the imine nitrogen atom (animine nitrogen group). Additionally, the present application may referto substituents/groups/atoms attached to the acyl carbon atom of theα-acylimine group (an α-acylimine acyl carbon group),substituents/groups/atoms attached to the imine carbon atom of theα-acylimine group (an α-acylimine imine carbon group), and/orsubstituent(s)/group(s)/atom(s) attached to the imine nitrogen atom ofthe α-acylimine group (an α-acylimine nitrogen group). For the purposeof this application the —C═N— portion of a pyridine ring, or pyridinecontaining ring system (shown in its localized or delocalized form) doesnot constitute an imine group.

For purposes of this application, a “hydrocarbyl group” has thedefinition specified by IUPAC: a univalent group formed by removing ahydrogen atom from a hydrocarbon (i.e. a group containing only carbonand hydrogen). A hydrocarbyl group can include the term “alkyl” or“alkyl group.” A hydrocarbyl group can include rings, ring systems,aromatic rings, and aromatic ring systems which contain only carbon andhydrogen.

For purposes of this application, an “organyl group” has the definitionspecified by IUPAC: an organic substituent group, regardless offunctional type, having one free valence at a carbon atom. Thus, anorganyl group can contain organic functional groups and/or atoms otherthan carbon and hydrogen (i.e. an organic group that can comprisefunctional groups and/or atoms in addition to carbon and hydrogen). Forexample, non-limiting examples of atoms other than carbon and hydrogeninclude halogens, oxygen, nitrogen, and phosphorus, among others.Non-limiting examples of functional groups include ethers, aldehydes,ketones, aldehydes, esters, sulfides, amines, and phosphines, amongothers. Included in the organyl group definition are heteroatomcontaining rings, heteroatom containing ring systems, heteroaromaticrings, and heteroaromatic ring systems. Finally, it should be noted thatthe organyl group definition includes the organyl group consisting ofinert functional groups, and the hydrocarbyl group as a members.

For the purposes of this application, the term or variations of the term“organyl group consisting of inert functional groups” refers to anorganyl group wherein the organic functional groups and/or atoms otherthan carbon and hydrogen present in the functional group are restrictedto those functional group and/or atoms other than carbon and hydrogenwhich do not complex with a metal salt and/or are inert under theprocess conditions defined herein. Thus, the term or variation of theterm “organyl groups consisting of inert functional groups” furtherdefines the particular organyl groups that can be present within theorganyl group consisting of inert functional groups. Additionally, theterm “organyl group consisting of inert functional groups” can refer tothe presence of one or more inert functional groups within the organylgroup. The term or variation of the “organyl group consisting of inertfunctional group” definition includes the hydrocarbyl group as a member.

For purposes of this application, an “inert functional group” is a groupwhich does not substantially interfere with any process described hereinin which it takes part and/or does not complex with the metal salt of anα-diimine metal complex. The term “does not complex with the metal salt”can include groups that could complex with a metal salt but inparticular molecules described herein can not complex with a metal saltdue to its positional relationship within a complexing α-diimine group.For example, while an ether group can complex with a metal salt, anether group located at a para position of a substituted phenyl iminenitrogen group is an inert functional group because a single metal saltmolecule can not complex with both the ether group and the imine groupof the α-diimine compound within the same molecule. Thus, the inertnessof a particular functional group is not only related to its functionalgroup's inherent inability to complex the metal salt but can also berelated to the functional group's position within the metal complex.Non-limiting examples of inert functional groups which due notsubstantially interfere with any process described herein can includehalo (fluoro, chloro, bromo and iodo), ethers (alkoxy group or etherylgroup), sulfides (sulfidyl group), and/or hydrocarbyl groups.

The terms “polymerized product having X carbon atoms” and “oligomerizedproduct having X carbon atoms,” wherein X can be any integer, refers tomaterials produced in a reactor by monomer polymerization or monomeroligomerization that has X carbon atoms. Thus, the term polymerizedproduct having X carbon atoms and oligomerized product having X carbonatoms excludes materials in the reactor effluent having X carbon atomswhich were not polymerized or oligomerized (e.g. solvent).

For purposes of this application, a primary carbon group is —CH₃.

For purposes of this application, a secondary carbon group includes agroup of the formula —CH₂—, wherein the one free valence (−) is to anatom other than a hydrogen atom (the bond represented by the dash, —, isto atom and/or group to which the secondary carbon group is attached).Thus, the free valence can be bonded to a halogen atom, carbon atom,oxygen atom, sulfur atom, etc. In other words, the free valence can beto an organyl group, an organyl group consisting of inert functionalgroups, a hydrocarbyl group, a functional group, or an inert functionalgroup. Non-limiting examples of secondary carbon groups include—CH₂CH(CH₃)₂, —CH₂Cl, —CH₂C₆H₅, and —CH₂OCH₃.

For purposes of this application, a tertiary carbon group includes agroup of the formula —CH═, wherein the two free valences (═) are toatoms other than a hydrogen atom (the bond represented by the dash, —,is to atom and/or group to which the tertiary carbon group is attached).Thus, the two free valences can be independently bonded to a halogenatom, carbon atom, oxygen atom, sulfur atom, etc. In other words, eachof the two free valences can be to an organyl group, an organyl groupconsisting of inert functional groups, a hydrocarbyl group, a functionalgroup, or an inert functional group. Non-limiting examples of secondarycarbon groups include —CH(CH₃)₂, —CHCl₂, —CH(C₆H₅)₂, -cyclohexyl,—CH(CH₃)OCH₃, and —CH═CHCH₃.

For purposes of this application, a quaternary carbon group includes agroup of the formula —C≡, wherein the three free valences, ≡, are toatoms other than a hydrogen atom (the bond represented by the dash, —,is to atom and/or group to which the quaternary carbon group isattached). Thus, each of the three free valences can be independentlybonded to a halogen atom, carbon atom, oxygen atom, sulfur atom, etc. Inother words, each of the three free valences can be to an organyl group,an organyl group consisting of inert functional groups, a hydrocarbylgroup, a functional group, or an inert functional group. Non-limitingexamples of tertiary carbon groups include: —C(CH₃)₃, —C(C₆H₅)₃, —CCl₃,—C(CH₃)₂OCH₃, —C≡ CH, —C(CH₃)CH═CH₂, —C₆H₅, —CF₃, and -1-adamantyl.

α-Diimine Metal Complex, Starting Materials, and Intermediates

Generally, the α-diimine metal complexes can be prepared from α-diacylcompounds, two primary amines, and a metal salt. Within the methods toprepare the α-diimine metal complexes, additional compounds includingα-acylimine compounds and α-acylimine metal complexes can beintermediates and/or starting materials in the synthesis of theα-diimine metal complexes. The α-diacyl compounds, primary amines,α-acylimine compounds, α-acylimine metal complexes, and metal salts areindependent elements within the α-diimine metal complex synthesis andfurther described herein.

α-Diacyl Compounds

Generally, α-diacyl compounds utilized in the production of theα-diimine metal complexes comprise two acyl groups capable of forming animine group when contacted with a primary amine. Appropriate α-diacylcompounds can be those capable of reacting with two primary amines toform an α-diimine compound. Within in this specification, the term“capable of reacting with two primary amines to form an α-diiminecompound” should not be construed to mean that two primary amines arenecessarily added in the same step. Nor should the term be construed tomean that an α-diimine compound is necessarily formed as an intermediateto an α-diimine metal complex. Further, defining an α-diacyl compound asone capable of forming an imine group when contacted with a primaryamine is not necessarily indicative of methods of forming an iminegroup. The term “capable of reacting with two primary amines to form anα-diimine compound” is intended to describe to one skilled in the artthe particular α-diacyl compounds which can be utilized in the synthesisof the α-diimine metal complexes described herein. The α-diimine metalcomplexes can be produced utilizing any method as described herein.

One class of α-diacyl compounds that can be used in preparing α-diiminemetal complexes is an α-ketoaldehyde, which is a compound wherein aketone oxygen atom and an aldehyde oxygen atom are bonded to adjacentcarbon atoms. The α-ketoaldehydes utilized in the production of theα-diimine metal complexes can be any α-ketoaldehyde capable of reactingwith two primary amines to form an α-diimine compound. Theα-ketoaldehyde can be saturated, unsaturated, linear, branched, acyclic,cyclic, aromatic, and/or heteroaromatic.

Generally, the α-ketoaldehyde will have the structure R^(ka)—C(═O)C(═O)Hwherein R^(ka) can be an organyl group, an organyl group consisting ofinert functional groups, or a hydrocarbyl group. In some embodiments,R^(ka) is an organyl group; alternatively, an organyl group consistingof inert functional groups; or alternatively, a hydrocarbyl group.Generally, R^(ka) can be a C₁ to C₃₀ organyl group; alternatively, a C₁to C₃₀ organyl group consisting of inert functional groups;alternatively, a C₁ to C₃₀ hydrocarbyl group; alternatively, a C₁ to C₂₀organyl group; alternatively, a C₁ to C₂₀ organyl group consisting ofinert functional groups; alternatively, a C₁ to C₂₀ hydrocarbyl group;alternatively, a C₁ to C₁₀ organyl group; alternatively, a C₁ to C₁₀organyl group consisting of inert functional groups; alternatively, a C₁to C₁₀ hydrocarbyl group; alternatively, a C₁ to C₅ organyl group;alternatively, a C₁ to C₅ organyl group consisting of inert functionalgroups; or alternatively, a C₁ to C₅ hydrocarbyl group. Generally theorganyl group, organyl group consisting of inert functional groups, orhydrocarbyl group of the α-ketoaldehyde can be saturated, unsaturated,acyclic, cyclic, linear, branched, and/or aromatic.

In some embodiments, R^(ka) represents an acyclic organyl group, anacyclic organyl group consisting of inert functional groups, or anacyclic hydrocarbyl group. In other embodiments, R^(ka) represents acyclic organyl group, a cyclic organyl group consisting of inertfunctional groups, or cyclic hydrocarbyl group. Regardless of thestructure of the organyl group, organyl group consisting of inertfunctional groups, or hydrocarbyl group, R^(ka) can have any number ofcarbon atoms as indicated herein. In some embodiments, theα-ketoaldehyde is a C₃ to C₂₀ glyoxal; alternatively, a C₃ to C₁₀glyoxal; or alternatively, a C₃ to C₆ glyoxal. In some embodiments, theα-ketoaldehyde is phenylglyoxal or a substituted phenylglyoxal. In otherembodiments, the α-ketoaldehyde is phenylglyoxal. Within substitutedphenylglyoxal, each substituent can be a C₁ to C₅ organyl groups, a C₁to C₅ organyl groups consisting of inert functional groups, and/or a C₁to C₅ hydrocarbyl groups. In other embodiments, each phenyl substituentscan be a C₁ to C₅ organyl groups consisting of inert functional groups;or alternatively, a C₁ to C₅ hydrocarbyl groups.

A second class of α-diacyl compounds which can be used in preparingα-diimine metal complexes is an α-dione (a compound wherein two ketoneoxygen atoms are bonded to adjacent carbon atoms). The α-diones utilizedin the production of the α-diimine metal complexes can be any α-dionecompound capable of reacting with two primary amines to form anα-diimine compound. The α-dione can be saturated, unsaturated, acyclic,cyclic, linear, branched, aromatic, and/or heteroaromatic.

Generally, the α-dione will have the structure R^(k1)—C(═O)—C(═O)—R^(k2)wherein the structures of R^(k1) and R^(k2) are independent of eachother and can be an organyl group, an organyl group consisting of inertfunctional groups, or a hydrocarbyl group. In embodiments, R^(k1) and/orR^(k1) can be a C₁ to C₃₀ organyl group; alternatively, a C₁ to C₃₀organyl group consisting of inert functional groups; alternatively, a C₁to C₃₀ hydrocarbyl group; alternatively, a C₁ to C₂₀ organyl group;alternatively, a C₁ to C₂₀ organyl group consisting of inert functionalgroups; alternatively, a C₁ to C₂₀ hydrocarbyl group; alternatively, aC₁ to C₁₀ organyl group; alternatively, C₁ to C₁₀ organyl groupconsisting of inert functional groups; alternatively, a C₁ to C₁₀hydrocarbyl group; alternatively, a C₁ to C₅ organyl group;alternatively, a C₁ to C₅ organyl group consisting of inert functionalgroups; or alternatively, a C₁ to C₅ hydrocarbyl group.

In some embodiments, the α-dione is an acyclic α-dione; both R^(k1) andR^(k2) are acyclic. In other embodiments, α-dione can be a semi-cyclicα-dione; R^(k1) and/or R^(k2) are, or comprise, a cyclic structure butare not connected through a ring or ring system. In yet otherembodiments, the α-dione is a cyclic α-dione; R^(k1) and R^(k2) areconnected to form a ring or ring system containing both carbon atoms ofthe α-dione group. In some semi-cyclic and/or cyclic α-dioneembodiments, the ring or ring system can be saturated. In othersemi-cyclic and/or cyclic α-dione embodiments, the ring or ring systemcan contain carbon-carbon double bonds. In further semi-cyclic and/orcyclic α-dione embodiments, the ring system can be a bicyclic ringsystem. In yet other semi-cyclic and/or cyclic α-dione embodiments, thering or ring system can comprise an aromatic ring or an aromatic ringstructure.

In acyclic α-dione embodiments, the α-dione can be 2,3-butanedione, asubstituted 2,3-butanedione, 2,3-pentanedione, a substituted2,3-pentanedione, 2,3-hexanedione, a substituted 2,3-hexanedione,3,4-hexanedione, or a substituted 3,4-hexanedione. In some embodiments,the α-dione can be 2,3-butanedione, 2,3-pentanedione, 2,3-hexanedione,or 3,4-hexanedione. In further embodiments, the α-dione can be2,3-butanedione; alternatively, 2,3-pentanedione; alternatively,2,3-hexanedione; or alternatively, 3,4-hexanedione.

In aromatic semi-cyclic α-dione embodiments, the α-dione can be benzilor a substituted benzil. In other embodiments, the α-dione can bebenzil.

In saturated cyclic α-dione embodiments, the α-dione can be1,2-cyclobutanedione, a substituted 1,2-cyclobutanedione,1,2-cyclopentanedione, a substituted 1,2-cyclopentanedione,1,2-cyclohexanedione, a substituted 1,2-cyclohexanedione,1,2-cycloheptanedione, and a substituted 1,2-cycloheptanedione. In somesaturated cyclic α-dione embodiments, the α-dione can be1,2-cyclopentanedione, a substituted 1,2-cyclopentanedione,1,2-cyclohexanedione, or a substituted 1,2-cyclohexanedione. In somesaturated cyclic α-dione embodiments, the α-dione can be1,2-cyclopentanedione, or 1,2-cyclohexanedione. In yet otherembodiments, the α-dione can be 1,2-cyclopentanedione; or alternatively,1,2-cyclohexanedione.

In saturated ring system α-dione embodiments, the α-dione can bebicyclo[2.2.1]hepta-1,2-dione, a substitutedbicyclo[2.2.1]hepta-1,2-dione, bicyclo[2.2.2]octa-1,2-dione, asubstituted bicyclo[2.2.2]octa-1,2-dione, or camphorquinone. In somesaturated ring system embodiments, the α-dione can bebicyclo[2.2.1]hepta-1,2-dione, bicyclo[2.2.2]octa-1,2-dione, orcamphorquinone. In yet other saturated ring system α-dione embodiments,the α-dione can be camphorquinone.

In unsaturated cyclic α-dione embodiments, the α-dione can be1,2-benzoquinone, a substituted 1,2-benzoquinone,cyclohex-3-ene-1,2-dione, a substituted cyclohex-3-ene-1,2-dione,cyclopent-3-ene-1,2-dione, a substituted cyclopent-3-ene-1,2-dione, acyclohex-4-ene-1,2-dione, a substituted cyclohex-4-ene-1,2-dione,3,4-dihydro-1,2-naphthoquinone, a substituted3,4-dihydro-1,2-naphthaquinone, 1,4-dihydronaphthoquinone, or asubstituted 1,4-dihydronaphthoquinone. In some unsaturated cyclicα-dione embodiments, the α-dione can be 1,2-benzoquinone,cyclohex-3-ene-1,2-dione, cyclopent-3-ene-1,2-dione,cyclohex-4-ene-1,2-dione, 3,4-dihydronaphthoquinone, or1,4-dihydronaphthoquinone. In other unsaturated ring α-dioneembodiments, the α-dione can be 1,2-benzoquinone; alternatively,3,4-dihydronaphthoquinone; or alternatively,1,4-dihydronaphthano-quinone.

In aromatic ring system α-dione embodiments, the α-dione can be a1,2-naphthoquinone, a substituted 1,2-naphthoquinone,2,3-naphthoquinone, a substituted 2,3-naphthoquinone,acenaphthenequinone, a substituted acenaphthenequinone,phenanthrenequinone, a substituted phenanthrenequinone, pyrenequinone,or a substituted pyrenequinone. In some aromatic ring system α-dioneembodiments, the α-dione can be 1,2-naphthoquinone, 2,3-naphthoquinone,acenaphthenequinone, phenanthrenequinone, or pyrenequinone. In otheraromatic ring system α-dione embodiments, the α-dione can beacenaphthenequinone, phenanthrenequinone, or pyrenequinone. In yet otheraromatic ring system α-dione embodiments, the α-dione can be1,2-naphthoquinone; alternatively, 2,3-naphthoquinone; alternatively,acenaphthenequinone; alternatively, phenanthrenequinone; oralternatively, pyrenequinone.

Within the substituted α-dione embodiments, each substituent canindependently be an organyl group, an organyl group consisting of inertfunctional groups, a hydrocarbyl group, or an inert functional group. Insome embodiments, the organyl substituent(s) can be a C₁ to C₂₀ organylgroup, a C₁ to C₂₀ organyl group consisting of inert functional groups,or a C₁ to C₂₀ hydrocarbyl group. In some substituted α-dioneembodiments, the substituents can be a C₁ to C₁₀ organyl group, a C₁ toC₁₀ organyl group consisting of inert functional groups, or a C₁ to C₁₀hydrocarbyl group. In other substituted α-dione embodiments, thesubstituent(s) can be a C₁ to C₅ organyl group, a C₁ to C₅ organyl groupconsisting of inert functional groups, or a C₁ to C₅ hydrocarbyl group.In further substituted α-dione embodiments, the substituent(s) can be aC₁ to C₂₀ organyl group; alternatively, a C₁ to C₁₀ organyl group;alternatively, a C₁ to C₅ organyl group; alternatively, a C₁ to C₂₀organyl group consisting of inert functional groups; alternatively, a C₁to C₁₀ organyl group consisting of inert functional groups;alternatively, a C₁ to C₅ organyl group consisting of inert functionalgroups; alternatively, a C₁ to C₂₀ hydrocarbyl group; alternatively, aC₁ to C₁₀ hydrocarbyl group; alternatively, a C₁ to C₅ hydrocarbylgroup; or alternatively, an inert functional group. Independent of thecarbon number of the organyl group, organyl group consisting of inertfunctional groups, and hydrocarbyl group, each organyl group, organylgroup consisting of inert functional groups, and hydrocarbyl groupsubstituent can be a primary, secondary, tertiary, or quaternaryhydrocarbyl group. In some embodiments, each organyl group, organylgroup consisting of inert functional groups, and hydrocarbyl group canbe a primary group; alternatively, a secondary group; alternatively, atertiary group; or alternatively, a quaternary group. Independent of thecarbon number of the organyl group consisting of inert functionalgroups, the organyl group consisting of inert functional groups cancomprise a halides, ether groups, or sulfide groups. In someembodiments, the organyl group consisting of inert functional groups canbe a trifluoromethyl group; or alternatively, a trichloromethyl group.Independent of the carbon number of the hydrocarbyl group, eachhydrocarbyl group substituent can independently be a methyl, ethyl,n-propyl (1-propyl), isopropyl (2-propyl), n-butyl (1-butyl), sec-butyl(2-butyl), isobutyl (2-methyl-1-propyl), tert-butyl (2-methyl-2-propyl),n-pentyl (1-pentyl), 2-pentyl, 3-pentyl, 2-methyl-1-butyl, tert-pentyl(2-methyl-2-butyl), 3-methyl-1-butyl, 3-methyl-2-butyl, neo-pentyl(2,3-dimethyl-1-propyl), or n-hexyl (1-hexyl) group. In embodiments, theinert functional group can be a halogen atom or an alkoxy group;alternatively, a halogen atom; or alternatively, an alkoxy group. Insome embodiments, the halogen atom may be fluorine, chlorine, bromine oriodine; alternatively, chlorine; or alternatively, fluorine. In someembodiments, the alkoxy group can be a methoxy group; alternatively, anethoxy group; alternatively, an isopropoxy group; or alternatively, atert-butoxy group.

In embodiments, the α-diacyl compounds can have any Structure asindicated in Table 1. In other embodiments, the diacyl compound can haveStructure 2, 3, 4, or 5; alternatively, Structure 6; alternatively,Structure 7, 8, or 9; alternatively, structure 10, 11, or 12; oralternatively, Structure 10. TABLE 1 Example α-Diacyl Compounds

Within the Structures of Table 1, R¹, R², R¹¹ to/through R²⁰, R³¹to/through R⁴³, and R⁵¹ to/through R⁶⁰ can each independently behydrogen, an organyl group, an organyl group consisting of inertfunctional groups, or a hydrocarbyl group. The organyl group, organylgroup consisting of inert functional groups, and hydrocarbyl group aregenerally described within the description of the α-diacyl compounds andcan have any embodiment as described therein. In Structure 2, “p” can bea whole integer ranging from 1 to 10; alternatively, a whole integerranging from 1 to 3; alternatively, 1; alternatively, 2; oralternatively, 3. In some embodiments, R¹, R², R¹¹ to/through R²⁰, R³¹to/through R⁴³, and R⁵¹ to/through R⁶⁰ can be hydrogen. In someembodiments, the α-diacyl compound may have Structure 1 where R¹ is anorganyl group, an organyl group consisting of inert functional groups,or a hydrocarbyl group, and R² is hydrogen.

Primary Amines

The primary amine(s) that can be utilized in the synthesis of theα-diimine metal complexes (and/or the intermediate α-acyliminecompounds, α-acylimine metal complexes) can be any primary amine capableof forming an imine group when contacted with an acyl group. It shouldbe noted that while the applicable primary amines are described in termsof the ability to form an imine group when contacted with an acyl group,such description is not intended to imply a method by which an iminegroup of an α-acylimine compound, α-acylimine metal complex, α-diiminecompound, and/or α-diimine metal complex described herein are made. Thelanguage is intended to describe, to one skilled in the art, theparticular primary amine(s) that can be utilized in the synthesis of anα-acylimine compound, α-acylimine metal complex, α-diimine compound,and/or α-diimine metal complex as described herein. The α-acyliminecompound, α-acylimine metal complex, α-diimine compound, and/orα-diimine metal complexes can be produced using any method describedherein.

Minimally, the primary amine comprises an —NH₂ group. In a furtherembodiment, the primary amine comprises an —NH₂ group and an organylgroup; alternatively, comprises an —NH₂ group and a metal saltcomplexing group; alternatively, comprises an —NH₂ group, a metal saltcomplexing group and a linking group linking the metal salt complexinggroup to the —NH₂ group; alternatively, comprises an —NH₂ group and anorganyl group consisting of inert functional groups; or alternatively,comprises an —NH₂ group and a hydrocarbyl group. In yet otherembodiments, the primary amine consists of an —NH₂ group and an organylgroup; alternatively, consists of an —NH₂ group, a metal salt complexinggroup and a linking group linking the metal salt complexing group to the—NH₂ group; alternatively, consists of an —NH₂ group and an organylgroup consisting of inert functional groups; or alternatively, consistsof an —NH₂ group and a hydrocarbyl group. The primary amines can besaturated, unsaturated, linear, branched, acyclic, cyclic, aromatic,and/or heteroaromatic.

In an aspect, the primary amine can comprise an —NH₂ group and organylgroup; or alternatively, the primary amine can consist of an —NH₂ groupand an organyl group. In the embodiments wherein the primary amine cancomprise or consist of an —NH₂ group and organyl group, the organylgroup can be a C₁ to C₃₀ organyl group; alternatively, a C₁ to C₂₀organyl group; alternatively, a C₁ to C₁₀ organyl group; oralternatively, a C₁ to C₅ organyl group. The organyl group can besaturated, unsaturated, linear, branched, acyclic, cyclic, aromatic,and/or heteroaromatic. In some embodiments, the primary amine comprisingor consisting of an —NH₂ group and organyl groups can have Structure 1aindicated below:R^(a1)NH₂   Structure 1awherein R^(a1) represents the organyl group. In embodiments, thatutilize a second primary amine comprising or consisting of an —NH₂ groupand organyl groups, the second primary amine comprising or consisting ofan —NH₂ group and organyl groups can be designated as having Structure2a indicated below:R^(a1′)NH₂   Structure 2awherein R^(a1′) represents the organyl group.

In an aspect, the primary amine can comprise an —NH₂ group and anorganyl group consisting of inert functional groups; or alternatively,the primary amine can consist of an —NH₂ group and an organyl groupconsisting of inert functional groups. In the embodiments wherein theprimary amine can comprise or consist of an —NH₂ group and an organylgroup consisting of inert functional groups, the organyl groupconsisting of inert functional groups can be a C₁ to C₃₀ organyl groupconsisting of inert functional groups; alternatively, a C₁ to C₂₀organyl group consisting of inert functional groups; alternatively, a C₁to C₁₀ organyl group consisting of inert functional groups; oralternatively, a C₁ to C₅ organyl group consisting of inert functionalgroups. The organyl group consisting of inert functional groups can besaturated, unsaturated, linear, branched, acyclic, cyclic, aromatic,and/or heteroaromatic. In some embodiments, the inert functional groupscan be ether groups; alternatively, sulfide groups; alternatively,halide atoms; or alternatively, hydrocarbyl groups. In some embodiments,the primary amine comprising or consisting of an —NH₂ group and anorganyl group consisting of inert functional groups can have Structure1a wherein R^(a1) represents the organyl group consisting of inertfunctional groups. In embodiments that utilize a second primary aminecomprising or consisting of an —NH₂ group and an organyl groupconsisting of inert functional groups, the second primary aminecomprising or consisting of an —NH₂ group and an organyl groupconsisting of inert functional groups can be designated as havingStructure 2a wherein R^(a1′) represents the organyl group consisting ofinert functional groups.

In some embodiments, the organyl group consisting of inert functionalgroups can be an aromatic ring or aromatic ring system having one ormore inert functional group substituent(s). In these embodiments, thearomatic ring or aromatic ring system can be a substituted benzene ring(a substituted phenyl group); or alternatively, a substitutednaphthalene ring (a substituted naphthyl group). The aromatic ring oraromatic ring system inert functional group substituent(s) can be anorganyl group having halogen atoms, an ether group (alkoxy group oretheryl group), or a sulfide group (sulfidyl group). In someembodiments, the aromatic ring inert functional group substituent(s) canbe a trifluoromethyl group, a C₁ to C₅ ether group a C₁ to C₅ sulfidegroup or a halogen atom. In some embodiments, the halogen atom may befluorine, chlorine, bromine or iodine; alternatively, chlorine; oralternatively, fluorine. In some embodiments, the alkoxy group can be amethoxy group; alternatively, an ethoxy group; alternatively, anisopropoxy group; or alternatively, a tert-butoxy group. Non-limitingexamples of a primary amine consisting of an aromatic ring having one ormore inert functional groups include substituted anilines wherein thesubstituents can be the substituents as described above. Non-limitingexamples are primary amines consisting of an aromatic ring or aromaticring systems having one or more inert functional groups such as2-methoxyaniline, 3-methoxyaniline, 4-methoxyanaline, 2-chloroaniline,3-chloroaniline, 4-chloroanaline, 2-fluoroaniline, 3-fluoroaniline,4-fluoroanaline, 2,6-trifluoromethylaniline, ordimethyl-4-methoxyaniline.

In some embodiments, a primary amine comprising or consisting of an —NH₂group and an organyl group consisting of inert functional groups canhave Structure 3a as indicated below:

wherein R^(a11) to/through R^(a15) represent the substituents of thearomatic ring. In embodiments that utilize a second primary aminecomprising or consisting of an —NH₂ group and an organyl groupconsisting of inert functional groups, the second primary aminecomprising or consisting of an —NH₂ group and an organyl groupconsisting of inert functional groups can be designated as havingStructure 4a indicated below:

wherein R^(a11′) to/through R^(a15′) represent the substituents of thearomatic ring.

In an aspect, the primary amine can comprise an —NH₂ group andhydrocarbyl group; or alternatively, the primary amine can consist of an—NH₂ group and a hydrocarbyl group. In embodiments wherein the primaryamine can comprise or consist of an —NH₂ group and hydrocarbyl group,the hydrocarbyl group can be a C₁ to C₃₀ hydrocarbyl group;alternatively, a C₁ to C₂₀ hydrocarbyl group; alternatively, a C₁ to C₁₀hydrocarbyl group; or alternatively, a C₁ to C₅ hydrocarbyl group.Independently, the hydrocarbyl group can be a saturated, unsaturated,acyclic, cyclic, linear, branched, and/or aromatic. In some embodiments,the primary amine comprising or consisting of an —NH₂ group and ahydrocarbyl group can have Structure 1a wherein R^(a1) represents thehydrocarbyl group. In embodiments that utilize a second primary aminecomprising or consisting of an —NH₂ group and an hydrocarbyl group, thesecond primary amine comprising or consisting of an —NH₂ group and anhydrocarbyl group can be designated as having Structure 2a whereinR^(a1′) represents the hydrocarbyl group.

Acyclic hydrocarbyl group embodiments can include C₁ to C₃₀ acyclichydrocarbyl groups; alternatively, C₁ to C₂₀ acyclic hydrocarbyl groups;alternatively, C₁ to C₁₀ acyclic hydrocarbyl groups; or alternatively,C₁ to C₅ acyclic hydrocarbyl groups. The acyclic hydrocarbyl groups canbe linear; or alternatively, branched. Independent of the carbon numberof the acyclic hydrocarbyl group, the acyclic hydrocarbyl group can be aprimary, secondary, tertiary, or quaternary hydrocarbyl group. In someembodiments, the acyclic hydrocarbyl group can be a primary hydrocarbylgroup; alternatively, a secondary hydrocarbyl group; alternatively, atertiary hydrocarbyl group; or alternatively, a quaternary hydrocarbylgroup. In an aspect, the acyclic hydrocarbyl groups can be a methyl,ethyl, n-propyl (1-propyl), isopropyl (2-propyl), n-butyl (1-butyl),sec-butyl (2-butyl), isobutyl (2-methyl-1-propyl), tert-butyl(2-methyl-2-propyl), n-pentyl (1-pentyl), 2-pentyl, 3-pentyl,2-methyl-1-butyl, tert-pentyl (2-methyl-2-butyl), 3-methyl-1-butyl,3-methyl-2-butyl, neo-pentyl (2,3-dimethyl-1-propyl), or n-hexyl(1-hexyl) group. Specific, non-limiting, examples of primary aminesconsisting of an —NH₂ group and an acyclic hydrocarbyl groups includemethyl amine, ethyl amine, n-propylamine, isopropyl amine, n-butylamine, sec-butylamine (2-butylamine), isobutylamine(2-methyl-1-propylamine), tert-butylamine (2-methyl-2-propylamine),n-pentylamine, neopentylamine, and n-hexylamine. One skilled in the artwill readily recognize which hydrocarbyl groups belong (and which amineshave a hydrocarbyl group that belongs) to the primary, secondary,tertiary, or quaternary hydrocarbyl group classes.

Cyclic hydrocarbyl group embodiments can include embodiments wherein thehydrocarbyl group is cyclic (the —NH₂ group is attached to a carbon thatis a member of a ring or ring system) or embodiments wherein thehydrocarbyl group comprises a cyclic group (the —NH₂ group is attachedto a carbon atom that is not a member of a ring or ring system).Regardless of whether the cyclic hydrocarbyl group is cyclic orcomprises a cyclic group, the cyclic hydrocarbyl group can be C₄ to C₃₀cyclic hydrocarbyl group; alternatively, a C₄ to C₂₀ cyclic hydrocarbylgroup; or alternatively, a C₄ to C₁₀ cyclic hydrocarbyl group. Inembodiments, the cyclic hydrocarbyl group can comprise a cyclobutylgroup, a substituted cyclobutyl group, a cyclopentyl group, asubstituted cyclopentyl group, a cyclohexyl group, a substitutedcyclohexyl group, a cycloheptyl group, a substituted cycloheptyl group,an adamantyl group, or a substituted adamantyl group. In someembodiments, the cyclic hydrocarbyl group can be a cyclobutyl group;alternatively, a cyclopentyl group; alternatively, a cyclohexyl group;alternatively, a cycloheptyl, or alternatively, an adamantyl group. Insome embodiments, the primary amine comprising an —NH₂ group and cyclichydrocarbyl group can be a substituted cyclopentylamine, a substitutedcyclohexylamine, a substituted cyclohexylamine, or a substitutedadamantylamine. In other embodiments, the primary amine comprising orconsisting of an —NH₂ group and cyclic hydrocarbyl group can be asubstituted cyclopentylamine; alternatively, a substitutedcyclohexylamine; or alternatively, a substituted adamantylamine. In yetother embodiments, the primary amine comprising or consisting of an —NH₂group and cyclic hydrocarbyl group can be cyclopentylamine,cyclohexylamine, cycloheptylamine, or adamantylamine. In yet otherembodiments, the primary amine consisting of a cyclic hydrocarbyl groupcan be cyclopentylamine; alternatively, cyclohexylamine; oralternatively, adamantylamine.

Aromatic hydrocarbyl group embodiments can include embodiments whereinthe hydrocarbyl group is aromatic (the —NH₂ group is attached to acarbon that is a member of an aromatic ring or ring system) orembodiments wherein the hydrocarbyl group comprises an aromatic group(the —NH₂ group is attached to a carbon atom that is not a member of aaromatic ring or aromatic ring system). Regardless of whether thearomatic hydrocarbyl group of the primary amine is aromatic or comprisesan aromatic group, the aromatic hydrocarbyl group can be a C₆ to C₃₀aromatic hydrocarbyl group; alternatively, a C₆ to C₂₀ aromatichydrocarbyl group; or alternatively, a C₆ to C₁₀ aromatic hydrocarbylgroup. In some embodiments, the aromatic hydrocarbyl group can be aphenyl group, substituted phenyl group, a naphthyl group, a substitutednaphthyl group, a benzyl group, or a substituted benzyl group. In otherembodiments, the aromatic hydrocarbyl group can be a phenyl group, anaphthyl group, or a benzyl group. In yet other embodiments, thearomatic hydrocarbyl group is a phenyl group; alternatively, a naphthylgroup; or alternatively, a benzyl group. In further embodiments, thearomatic hydrocarbyl group can be a substituted phenyl group;alternatively, a substituted naphthyl group; or alternatively, asubstituted benzyl group.

In embodiments, the primary amine comprising an —NH₂ group and anaromatic hydrocarbyl group can be aniline, a substituted aniline,1-naphthylamine, a substituted 1-naphthylamine, 2-naphthylamine, asubstituted 2-naphthylamine, benzyl amine, or a substituted benzylamine. In some embodiments, the primary amine comprising an —NH₂ groupand an aromatic hydrocarbyl group can be a substituted aniline, asubstituted 1-naphthylamine, a substituted 2-naphthylamine, or asubstituted benzyl amine. In other embodiments, the primary aminecomprising an —NH₂ group and an aromatic hydrocarbyl group can be asubstituted aniline; alternatively; a substituted 1-naphthylamine;alternatively, a substituted 2-naphthylamine; or alternatively, asubstituted benzyl amine. In other embodiments, the primary amineconsisting of an —NH₂ group and an aromatic hydrocarbyl group can beaniline, 1-naphthylamine, 2-naphthylamine, or benzyl amine. In yet otherembodiments, the primary amine can be aniline; 1-naphthylamime;alternatively, 2-napthylamine; or alternatively, benzyl amine. Infurther embodiments, the primary amine can be aniline, or a substitutedaniline. In embodiments, the substituted aniline can be substituted atthe 2-position. In some embodiments, the substituted aniline issubstituted at the 2- and 6-position; alternatively, at the 2- and5-position; or alternatively, at the 2-, 4-, and 6-positions. In otherembodiments, the substituents at the 2-position, at the 2- and6-position, at the 2- and 5-positions, or at the 2-, 4-, and 6-positionscan independently be a primary substituent; alternatively; a secondarysubstituent; alternatively, a tertiary substituent; or alternatively, aquaternary substituent. In some embodiments, the primary amineconsisting of an —NH₂ group and an aromatic hydrocarbyl group can be2,6-dimethylanaline, 2,6-diethylaniline, 2,6-diisopropylaniline, or2,6-di-tert-butylaniline. In other embodiments, the primary amineconsisting of an —NH₂ group and an aromatic hydrocarbyl group can be2,6-dimethylanaline, 2,6-diethylaniline, or 2,6-diisopropylaniline. Inyet other embodiments, the primary amine consisting of an —NH₂ group andan aromatic hydrocarbyl group can be 2,6-dimethylanaline; alternatively,2,6-diethylaniline; alternatively, 2,6-diisopropylaniline;alternatively, 2,6-di-tert-butylanaline; alternatively,2,5-di-tert-butylanaline; alternatively, 2-isopropyl-6-methylanaline; oralternatively, 2,4,6-trimethylanaline.

In some embodiments, the primary amine comprising or consisting of an—NH₂ group and an aromatic hydrocarbyl group can have Structure 3awherein R^(a11) to/through R^(a15) represent the substituents of thearomatic hydrocarbyl group. In embodiments that utilize a second primaryamine comprising or consisting of an —NH₂ group and an aromatichydrocarbyl group, the second primary amine comprising or consisting ofan —NH₂ group and an aromatic hydrocarbyl group can be designated ashaving Structure 4a wherein R^(a11′) to/through R^(a15′) represent thesubstituents of the aromatic hydrocarbyl group.

In embodiments, each substituent of the cyclic hydrocarbyl group or thearomatic hydrocarbyl group can independently be a C₁ to C₂₀ hydrocarbylgroup; alternatively, a C₁ to C₁₀ hydrocarbyl group; or alternatively, aC₁ to C₅ hydrocarbyl group. Independent of the carbon number of thecyclic hydrocarbyl substituent, the substituents of the cyclichydrocarbyl group or the aromatic hydrocarbyl group can be primary,secondary, tertiary, or quaternary hydrocarbyl groups. In someembodiments, a cyclic hydrocarbyl substituent or an aromatic hydrocarbylsubstituent can be a primary hydrocarbyl group; alternatively, asecondary hydrocarbyl group; alternatively, a tertiary hydrocarbylgroup; or alternatively, a quaternary hydrocarbyl group. In someembodiments, the cyclic hydrocarbyl group substituent or an aromatichydrocarbyl substituent can be a methyl, ethyl, n-propyl (1-propyl),isopropyl (2-propyl), n- butyl (1-butyl), sec-butyl (2-butyl), isobutyl(2-methyl-1-propyl), tert-butyl (2-methyl-2-propyl), n-pentyl(1-pentyl), 2-pentyl, 3-pentyl, 2-methyl-1-butyl,tert-pentyl(2-methyl-2-butyl), 3-methyl-1-butyl, 3-methyl-2-butyl,neo-pentyl(2,3-dimethyl-1-propyl), or n-hexyl (1-hexyl) group. Oneskilled in the art will readily recognize which cyclic hydrocarbyl groupsubstituents or aromatic hydrocarbyl substituents belong to the primary,secondary, tertiary, or quaternary hydrocarbyl group classes.

In substituted phenyl group embodiments, the substituted phenylhydrocarbyl group can be a 2-substituted phenyl group; alternatively, a2,6-disubstituted phenyl group; alternatively, a 2,5-disubstitutedphenyl group; or alternatively, a 2,4,6-trisubstituted phenyl group. Insome embodiments, the substituted phenyl hydrocarbyl group can be a2,6-dimethylphenyl group, a 2,6-diethylphenyl group, a2,6-diisopropylphenyl group, or a 2,6-di-tert-butylphenyl group. In yetother embodiments, the substituted phenyl hydrocarbyl group can be a2,6-dimethylphenyl group, a 2,6-diethylphenyl group, or a2,6-diisopropylphenyl group. In further embodiments, the substitutedphenyl hydrocarbyl group can be a 2,6-dimethylphenyl group;alternatively, a 2,6-diethylphenyl group; alternatively, a2,6-diisopropylphenyl group; alternatively, a 2,6-di-tert-butylphenylgroup; alternatively, a 2,5-di-tert-butylphenyl group; alternatively, a2-isopropyl-6-methyl group; or alternatively, a 2,4,6-trimethylphenylgroup (mesityl group).

In an embodiment, the primary amine can comprise an —NH₂ group and ametal salt complexing group. In another embodiment, the primary aminecan comprise an —NH₂ group, a metal salt complexing group, and a linkinggroup linking the metal salt complexing group to the —NH₂ group. In yetanother aspect the primary amine can consist of a metal salt complexinggroup, and a linking group linking the metal salt complexing group tothe —NH₂ group. Generally, the metal salt complexing group and thelinking group are independent elements. Thus, the primary aminecomprising or consisting of an —NH₂ group, a metal salt complexinggroup, and a linking group linking the metal salt complexing group tothe —NH₂ group can be described using any combination of the metal saltcomplexing group described herein and the linking group linking themetal salt complexing group to the —NH₂ group described herein,

In embodiments, the primary amine comprising or consisting of an —NH₂group, a metal salt complexing group, and a linking group linking themetal salt complexing group to the —NH₂ group can have Structure 5a:Q-L-NH₂   Structure 5awhere Q represents the metal salt complexing group and L represents thelinking group. In some embodiments, the metal salt complexing group andthe linking group can have structures indicated in Table 2 and Table 3,respectively.

The metal salt complexing group, Q, can be any group comprising aheteroatom capable of complexing with the metal salt. The linking group,L, can be any group capable of linking the metal salt complexing groupto the —NH₂ group. The linking group includes all atoms between theprimary amine nitrogen atom, the —NH₂, and the metal salt complexinggroup. If the metal salt complexing group is acyclic, the linking groupincludes all atoms between the primary amine nitrogen atom and theheteroatom of the metal salt complexing functional group. For example,in N,N-dimethylethylenediamine the linking group is —CH₂CH₂— and themetal salt complexing group is the N,N-dimethylaminyl group, and in2-phenoxyethylamine the linking group is —CH₂CH₂— and the metal saltcomplexing group is the phenoxy group. However, if the heteroatom of themetal salt complexing group is contained within a ring, the linkinggroup includes all the atoms between the primary amine nitrogen atom andthe first atom contained within the ring containing the metal saltcomplexing heteroatom of the metal salt complexing group. For example,in 2-(2-aminoethyl)pyridine the linking group is —CH₂CH₂— and the metalsalt complexing group is the 2-pyridinyl group, in1-(2-aminoethyl)piperidine the linking group is —CH₂CH₂— and the metalsalt complexing group is the 1-piperidinyl group, and in 2-aminopyridinethe linking group is a bond and the metal salt complexing group is the2-pyridinyl group.

The metal salt complexing group, Q, can be any group comprising aheteroatom capable of complexing with the metal salt. In embodiments,the metal salt complexing group can be a C₂ to C₃₀ group comprising aheteroatom; alternatively, a C₂ to C₂₀ group comprising a heteroatom;alternatively, a C₂ to C₁₀ group comprising a heteroatom; oralternatively, a C₂ to C₅ group comprising a heteroatom. In someembodiments, the metal salt complexing heteroatom of the metal saltcomplexing group can be oxygen, sulfur, nitrogen, or phosphorus. Inother embodiments, the metal salt complexing heteroatom of the metalsalt complexing group can be oxygen or sulfur. In yet other embodiments,the metal salt complexing heteroatom of the metal salt complexing groupcan be nitrogen, or phosphorus. In further embodiments, the metal saltcomplexing heteroatom of the metal salt complexing group can be oxygen;alternatively, sulfur; alternatively, nitrogen; or alternatively,phosphorus. Optionally, the metal salt complexing group can containadditional heteroatom which do not complex the metal salt in α-diiminemetal complex such as inert heteroatoms (e.g. halides, and silicon)and/or additional metal salt complexing heteroatom(s) which do notcomplex with the metal salt.

In particular embodiments, the metal salt complexing group can be adialkyl aminyl group, a diphenyl aminyl group, a substituted diphenylaminyl group, an alkyl phenyl aminyl group, an alkyl substituted phenylaminyl group, a dialkyl phosphinyl group, a diphenyl phosphinyl group, asubstituted diphenyl phosphinyl group, an alkyl phenyl phosphinyl group,an alkyl substituted phenyl phosphinyl group, an alkyl etheryl group, aphenyl etheryl group, a substituted phenyl etheryl group, an alkylsulfidyl group, a phenyl sulfidyl group, a substituted phenyl sulfidylgroup, a furanyl group, a substituted furanyl group, a thiophenyl group,a substituted thiophenyl group, a tetrahydrofuranyl group, a substitutedtetrahydrofuranyl group, a thiophanyl group, a substituted thiophanylgroup, a pyridinyl group, a substituted pyridinyl group, a morphilinylgroup, a substituted morphilinyl group, a pyranyl group, a substitutedpyranyl group, a tetrahydropyranyl group, a substitutedtetrahydropyranyl group, a quinolinyl group, a substituted quinolinylgroup, a pyrrolyl group, a substituted pyrrolyl group, a pyrrolidinylgroup, a substituted pyrrolidinyl group, a piperidinyl group, or asubstituted piperidinyl group. In embodiments, the metal salt complexinggroup can be a dialkyl aminyl group, a diphenyl aminyl group, a dialkylphosphinyl group, a diphenyl phosphinyl group, an alkyl etheryl group, aphenyl etheryl group, an alkyl sulfidyl group, a phenyl sulfidyl group,a furanyl group, a thiophenyl group, a tetrahydrofuranyl group, athiophanyl group, a pyridinyl group, a morphilinyl group, a pyranylgroup, a tetrahydropyranyl group, a quinolinyl group, a pyrrolyl group,a pyrrolidinyl group, or a piperidinyl group. In some embodiments, themetal salt complexing group can be a dialkyl aminyl group, a diphenylaminyl group, a substituted diphenyl aminyl group, a dialkyl phosphinylgroup, a diphenyl phosphinyl group, a substituted diphenyl phosphinylgroup, an alkyl etheryl group, a phenyl etheryl group, a substitutedphenyl etheryl group, an alkyl sulfidyl group, a phenyl sulfidyl group,a substituted phenyl sulfidyl group, a pyridinyl group, a substitutedpyridinyl group, a morphilinyl group, or a substituted morphilinylgroup; alternatively, a dialkyl aminyl group, a diphenyl aminyl group, adialkyl phosphinyl group, a diphenyl phosphinyl group, an alkyl etherylgroup, a phenyl etheryl group, an alkyl sulfidyl group, a phenylsulfidyl group, a pyridinyl group, or a morphilinyl group;alternatively, a dialkyl aminyl group, a diphenyl aminyl group, asubstituted diphenyl aminyl group, a dialkyl phosphinyl group, adiphenyl phosphinyl group, or a substituted diphenyl phosphinyl group;alternatively, a dialkyl aminyl group, a diphenyl aminyl group, adialkyl phosphinyl group, a diphenyl phosphinyl group; or alternatively,a diphenyl aminyl group, a substituted diphenyl aminyl group, a diphenylphosphinyl group, a substituted diphenyl phosphinyl group;alternatively, a diphenyl aminyl group, a substituted diphenyl aminylgroup, a diphenyl phosphinyl group, a substituted diphenyl phosphinylgroup, a phenyl sulfidyl group, a substituted phenyl sulfidyl group, apyridinyl group, or a substituted pyridinyl group; or alternatively, adiphenyl aminyl group, a diphenyl phosphinyl group, a phenyl sulfidylgroup, or a pyridinyl group. In other embodiments, the metal saltcomplexing group can be a dialkyl aminyl group or a dialkyl phosphinylgroup; alternatively, a diphenyl aminyl group or a diphenyl phosphinylgroup; alternatively, a substituted diphenyl aminyl group or asubstituted diphenyl phosphinyl group; alternatively, a 2-pyridinylgroup or a substituted 2-pyridinyl group; alternatively, an alkyletheryl group, a phenyl etheryl group, a substituted phenyl etherylgroup, a alkyl sulfidyl group, a phenyl sulfidyl group, or a substitutedsulfidyl group; alternatively, an alkyl etheryl group or an alkylsulfidyl group; alternatively, a phenyl etheryl group, a substitutedphenyl etheryl group, a phenyl sulfidyl group, or a substituted sulfidylgroup; alternatively, a phenyl etheryl group or a substituted phenyletheryl group; alternatively, a phenyl sulfidyl group, a substitutedphenyl sulfidyl group; alternatively, a phenyl sulfidyl group;alternatively, a substituted phenyl sulfidyl group; alternatively, afuranyl group, a substituted furanyl group, a thiophenyl group or asubstituted thiophenyl group; alternatively, a 1-morphilinyl group or asubstituted 1-morphilinyl group; alternatively, a 2-morphilinyl group ora substituted 2-morphilinyl group; alternatively, a 2-pyranyl group or asubstituted 2-pyranyl group; alternatively, a 2-tetrahydropyranyl group,a substituted 2-tetrahydropyranyl group; alternatively, a 1-piperidinylgroup, or a substituted 1-piperidinyl group; alternatively, a1-pyrrolidinyl group, a substituted 1-pyrrolidinyl group; alternatively,a 2-pyrrolidinyl group, a substituted 2-pyrrolidinyl group;alternatively, a 2-piperidinyl group, or a substituted 2-piperidinylgroup; alternatively, a 2-quinolinyl group or a substituted 2-quiolinylgroup; alternatively, a 1-pyrrolyl group or a substituted 1-pyrrolylgroup; alternatively, a 2-pyrrolyl group or a substituted 2-pyrrolylgroup; alternatively, a 2-tetrahydrofuranyl group or a substituted2-tetrahydrofuranyl group; or alternatively, a 2-thiophanyl group or asubstituted 2-thiophanyl group. In yet other embodiments, the metal saltcomplexing group can be a diphenyl aminyl group; alternatively, asubstituted diphenyl aminyl group; alternatively, a diphenyl phosphinylgroup; or alternatively, a substituted diphenyl phosphinyl group.

The alkyl group(s) of the aminyl, phosphinyl, ethyl, or sulfidyl metalsalt complexing group embodiments can independently be a C₁ to C₂₀organyl group consisting of inert functional groups; alternatively, a C₁to C₁₀ organyl group consisting of inert functional groups; oralternatively, a C₁ to C₅ organyl group consisting of inert functionalgroups; C₁ to C₂₀ hydrocarbyl group; alternatively, a C₁ to C₁₀hydrocarbyl group; or alternatively, a C₁ to C₅ hydrocarbyl group. Thesubstituted phenyl groups of the aminyl, phosphinyl, ethyl, or sulfidylmetal salt complexing group embodiments can independently be a C₆ to C₂₀phenyl group; or alternatively, a C₆ to C₁₅ phenyl group. Independently,the alkyl groups of the aminyl, phosphinyl, ethyl, or sulfidyl metalsalt complexing groups can be primary, secondary, tertiary, orquaternary hydrocarbyl groups. In some embodiments, the alkyl group ofthe aminyl, phosphinyl, ethyl, or sulfidyl metal salt complexing groupcan be a primary hydrocarbyl group; alternatively, a secondaryhydrocarbyl group; alternatively, a tertiary hydrocarbyl group; oralternatively, a quaternary hydrocarbyl group.

Each substituent of the substituted metal salt complexing groupembodiments can independently be a C₁ to C₁₀ organyl group, a C₁ to C₁₀organyl group consisting of inert functional groups, a C₁ to C₁₀hydrocarbyl group, or an inert functional group. In some embodiments,the substituents of the substituted metal salt complexing group can beC₁ to C₅ organyl groups, a C₁ to C₅ organyl groups consisting of inertfunctional groups, C₁ to C₅ hydrocarbyl groups, or an inert functionalgroup. In other embodiments, the substituents of the substituted metalsalt complexing group can be C₁ to C₁₀ organyl groups; alternatively, aC₁ to C₁₀ organyl groups consisting of inert functional groups;alternatively, a C₁ to C₁₀ hydrocarbyl groups; alternatively, a C₁ to C₅organyl groups; alternatively, a C₁ to C₅ hydrocarbyl groups; oralternatively, inert functional groups. Independent of the carbon numberof the organyl group, and the organyl group consisting of inertfunctional groups each organyl group and organyl group consisting ofinert functional groups can be a primary, secondary, tertiary, orquaternary hydrocarbyl group. In some embodiments, each organyl groupand organyl group consisting of inert functional groups can be a primarygroup; alternatively, a secondary group; alternatively, a tertiarygroup; or alternatively, a quaternary group. Independent of the carbonnumber of the organyl group consisting of inert functional groups, theorganyl group consisting of inert functional groups can comprise ahalide, an ether group (alkoxy group or etheryl group), or a sulfidegroup (sulfidyl group). In some embodiments, the organyl groupconsisting of inert functional groups can be a trifluoromethyl group; oralternatively, a trichloromethyl group. In embodiments, the inertfunctional group can be a halogen atom or an alkoxy group;alternatively, a halogen atom; or alternatively, an alkoxy group. Insome embodiments, the halogen atom may be fluorine, chlorine, bromine oriodine; alternatively, chlorine; or alternatively, fluorine. In someembodiments, the alkoxy group can be a methoxy group; alternatively, anethoxy group; alternatively, an isopropoxy group; or alternatively, atert-butoxy group.

Independent of the carbon number of the hydrocarbyl substituent, thealkyl group or the substituent(s) of the substituted metal saltcomplexing group can be a primary, secondary, tertiary, or quaternaryhydrocarbyl group. In some embodiments, the alkyl group or thesubstituent(s) of the substituted metal salt complexing group can be aprimary hydrocarbyl group; alternatively, a secondary hydrocarbyl group;alternatively, a tertiary hydrocarbyl group; or alternatively, aquaternary hydrocarbyl group. In some embodiments, the alkyl group orthe hydrocarbyl substituents of the substituted metal salt complexinggroup can be a methyl, ethyl, n-propyl(1-propyl), isopropyl(2-propyl),n-butyl(1-butyl), sec-butyl(2-butyl), isobutyl(2-methyl-1-propyl),tert-butyl(2-methyl-2-propyl), n-pentyl(1-pentyl), 2-pentyl, 3-pentyl,2-methyl-1-butyl, tert-pentyl(2-methyl-2-butyl), 3-methyl-1-butyl,3-methyl-2-butyl, neo-pentyl(2,3-dimethyl-1-propyl), or n-hexyl(1-hexyl)group. One skilled in the art will readily recognize which alkyl groupor the hydrocarbyl substituents of the substituted metal salt complexinggroup belong to the primary, secondary, tertiary, or quaternaryhydrocarbyl group classes.

The linking group linking the metal salt complexing group to the —NH₂group can be a bond, an organyl group, and organyl group consisting ofinert functional groups, or a hydrocarbyl group. In other embodiments,the linking group can be a bond; alternatively, an organyl group;alternatively, an organyl group consisting of inert functional groups;or alternatively, a hydrocarbyl group. In some embodiments, the linkinggroup can be a C₁ to C₁₀ organyl group; or alternatively, a C₁ to C₅organyl group. In some embodiments, the linking group linking the metalsalt complexing group to the —NH₂ group can be a C₁ to C₁₀ organyl groupconsisting of inert functional groups; or alternatively, a C₁ to C₅organyl group consisting of inert functional groups. In otherembodiments, the linking group linking the metal salt complexing groupto the —NH₂ group can be a C₁ to C₁₀ hydrocarbyl group; oralternatively, a C₁ to C₅ hydrocarbyl group.

In some embodiments, the hydrocarbyl linking group can be—(CR^(L)R^(L))_(m)— where R^(L) and R^(L) are independently hydrogen,methyl, ethyl, propyl, isopropyl, or butyl groups and m can be aninteger from 1 to 5. In other embodiments, the linking group can be amethylene group (—CH₂—), an ethylene group (—CH₂CH₂—), a propyl group(—CH₂CH₂CH₂—), a —CH(CH₃)CH₂— group, —C(CH₃)₂— group, or a butylenegroup (—CH₂CH₂CH₂—CH₂—). In some non-limiting embodiments, the linkinggroup can be a methylene group (—CH₂—), an ethylene group (—CH₂CH₂—), ora propylene group (—CH₂CH₂CH₂—); or alternatively, an ethylene group(—CH₂CH₂—), or a propylene group (—CH₂CH₂CH₂—). In yet otherembodiments, the linking group can be a methylene group; alternatively,an ethylene group; or alternatively, a propylene group.

In embodiments, the primary amine comprising a metal salt complexinggroup can be 1-(2-aminoethyl)pyrrolidine, 2-(2-aminoethyl)piperdine,2-(2-aminoethyl)pyrrolidine, N,N-dimethyl-ethylenediamine,N,N-diethylethylenediamine, N,N-diphenylethylenediamine,2-(aminomethyl)-pyridine, 2-(2-aminoethyl)pyridine,2-(diphenylphosphino)ethylamine, 3-(diphenylphosphino)-propylamine,2-(2-aminoethyl)furan, 2-(aminomethyl)furan, 2-(2-aminoethyl)thiophene,2-(aminomethyl)thiophene, 2-aminoethyl-(4-chlorophenyl)sulfide,2-phenoxyethylamine, 2-methoxy-ethylamine, 2-ethoxyethylamine,2-isopropxyethylamine, and 1-(2-aminoethyl)piperidine. In someembodiments, the primary amine comprising a metal salt complexing groupcan be N,N-dimethylethylenediamine, N,N-diethylethylenediamine,N,N-diphenylethylenediamine, 2-(amino-methyl)pyridine,2-(2-aminoethyl)pyridine, 2-(diphenylphosphino)ethylamine,3-(diphenyl-phosphino)propylamine, 2-aminoethyl-(4-chlorophenyl)sulfide,2-phenoxyethylamine, 2-methoxy-ethylamine, 2-ethoxyethylamine, 2-andisopropoxyethylamine. In yet other embodiments, the primary aminecomprising a metal salt complexing group can beN,N-dimethylethylenediamine or N,N-diethylethylenediamine;alternatively, N,N-diphenylethylenediamine,2-(diphenylphosphino)-ethylamine, 3-(diphenylphosphino)propylamine;alternatively, 2-(aminomethyl)pyridine, 2-(2-amino-ethyl)pyridine;alternatively, 2-aminoethyl-(4-chlorophenyl)sulfide; or alternatively,2-phenoxy-ethylamine, 2-methoxyethylamine, 2-ethoxyethylamine, and2-isopropxyethylamine. In further embodiments, the primary aminecomprising a metal salt complexing group can beN,N-dimethyl-ethylenediamine; alternatively, N,N-diethylethylenediamine;alternatively, N,N-diphenylethylene-diamine; alternatively,2-(diphenylphosphino)ethylamine; alternatively,3-(diphenylphosphino)-propylamine; alternatively,2-(aminomethyl)pyridine; alternatively, 2-(2-aminoethyl)pyridine; oralternatively, 2-aminoethyl-(4-chlorophenyl)sulfide.

In some embodiments, the metal salt complexing group can have anyStructure indicated in Table 2. In some embodiments, the metal saltcomplexing group can have Structure 1c or Structure 2c. In otherembodiments, the metal salt complexing group can have Structure 3c orStructure 4c; alternatively, Structure 5c or Structure 6c;alternatively, Structure 8c or Structure 9c; alternatively, TABLE 2Example Metal salt complexing Groups —OR^(c1) Structure 1c —SR^(c1)Structure 2c —NR^(c5)R^(c6) Structure 3c —PR^(c5)R^(c6) Structure 4c

Structure 11c or Structure 12c; alternatively, Structure 14c orStructure 15c; alternatively, Structure 19c or Structure 20c; oralternatively, Structure 21c or Structure 22c. In yet other embodiments,the metal salt complexing group can have Structure 3c; alternatively,Structure 4c; alternatively, Structure 7c; Structure 10c; alternatively,Structure 13c; alternatively, Structure 16c; alternatively, Structure17c; alternatively, Structure 18; alternatively, Structure 21c; oralternatively, Structure 22c.

Within the structures of Table 2, R^(c1), R^(c5), R^(c6), R^(c11)to/through R^(c21), R^(c31) to/through R^(c35), R^(c41) to/throughR^(c45), R^(c51) to/through R^(c54), R^(c61) to/through R^(c63), R^(c71)to/through R^(c80) can each independently be hydrogen, an organyl groupconsisting of inert functional groups, a hydrocarbyl group, or inertfunctional groups. In embodiments, R^(c1), R^(c5), R^(c6), R¹¹to/through R^(c20), R^(c31) to/through R^(c35), R^(c41) to/throughR^(c44), R^(c51) to/through R^(c54), R^(c61) to/through R^(c63), R^(c71)to/through R^(c80) of each Structure in Table 2 can independently behydrogen, an organyl group consisting of inert functional groups, ahydrocarbyl group, or an inert functional group and R^(c21) and R^(c45)can be a hydrocarbyl group. In some embodiments, R^(c1), R^(c5), R^(c6),R^(c11) to/through R^(c21), R^(c31) to/through R^(c35), R^(c41)to/through R^(c45), R^(c51) to/through R^(c54), R^(c61) to/throughR^(c63), R^(c71) to/through R^(c80) of each Structure of Table 2 anindependently be hydrogen, a C₁ to C₁₀ organyl group, a C₁ to C₁₀organyl group consisting of inert functional groups, a C₁ to C₁₀hydrocarbyl group, a C₁ to C₅ organyl group, a C₁ to C₅ organyl groupconsisting of inert functional groups, a C₁ to C₅ hydrocarbyl group oran inert functional group. The organyl groups, organyl groups consistingof inert functional groups, hydrocarbyl groups, and inert functionalgroups are generally described within the description of the metalcomplexing group descriptions and can have any embodiment as describedtherein.

In some embodiments, the linking group can have any structure indicatedin Table 3. Within the Structure of Table 3, the undesignated valanciesare the points of attachment for the —NH₂ group and the metal saltcomplexing group; each R^(L) can independently be hydrogen, a methylgroup, or an ethyl group; and m can be an integer ranging from 1 to 5.In further embodiments, m can be an integer ranging from 1 to 3;alternatively, m can be 2 or 3; alternatively, m can be 1;alternatively, m can be 2; or alternatively, m can be 3. TABLE 3 ExampleLinking Groups —(CR^(L)R^(L))_(m)— Structure 1L —(CH₂)_(m)— Structure 2L—(CH₂)— Structure 3L —(CH₂CH₂)— Structure 4L

In embodiments, the linking group can have Structure 1L, Structure 2L,Structure 3L, Structure 4L or Structure 5L. In some embodiments, thelinking group can have Structure 4L or Structure 5L. In otherembodiments, the linking group can have Structure 2L; alternatively,Structure 3L; alternatively, Structure 4L; or alternatively, Structure5L.

α-Acylimine Compounds

The α-acylimine compounds can be described using any one of severaldescriptions. While the α-acylimine compound descriptions may beindicated by labels such as first description, second description, etc.,these labels do not indicate a particular preference to the descriptionof the α-acylimine compounds.

In a first description, the α-acylimine compound can be minimallydescribed as a compound comprising an α-acylimine group. In furtherembodiments, the α-acylimine compound can be described as a compoundcomprising 1) an α-acylimine group and 2) an α-acylimine nitrogen group.In this first α-acylimine compound description, the α-acylimine groupcan be further described as being derived from an α-diacyl compound.Thus, alternatively, the α-acylimine compound can be described ascompound comprising 1) an α-acylimine group derived from an α-diacylcompound and 2) an α-acylimine nitrogen group; or alternatively, acompound consisting of 1) an α-acylimine group derived from an α-diacylcompound and 2) an α-acylimine nitrogen group.

Within the α-acylimine compound, the α-acylimine group's nitrogen atomis derived from the primary amine's —NH₂ group and the α-acyliminecompound's nitrogen group is derived from the remainder of the primaryamine. Thus, the α-acylimine nitrogen group can have any of theembodiments as the primary amine (with the absence of the —NH₂ group) asdescribed herein. Therefore, the organyl group, metal salt complexinggroup, linking group, organyl group consisting of inert functionalgroups, and hydrocarbyl groups of the primary amine embodimentsdescribed herein are generally applicable to the description of theα-acylimine compound's nitrogen group with the proviso that the linkinggroup links the metal salt complexing group to the imine nitrogen atomof the α-acylimine group instead of the —NH₂ group of the primary amine.Thus, in embodiments, the α-acylimine nitrogen group can comprise anorganyl group; alternatively, comprise a metal salt complexing group;alternatively, comprise a metal salt complexing group and a linkinggroup linking the metal salt complexing group to the α-acyliminenitrogen group nitrogen atom; alternatively, comprise an organyl groupconsisting of inert functional groups; alternatively, comprise ahydrocarbyl group; alternatively, consist of an organyl group;alternatively, consist of a metal salt complexing group and a linkinggroup linking the metal salt complexing group to the α-acyliminenitrogen group nitrogen atom; alternatively, consist of an organyl groupconsisting of inert functional groups; or alternatively, consist of ahydrocarbyl group. Additionally, as the α-acylimine group and theα-acylimine nitrogen group are derived from separate and independentelements, the α-diacyl compound and the primary amine, respectively, theα-acylimine compound can be further described using any combination ofthe α-diacyl compound element described herein and the elements of theprimary amine as described herein.

In a second description, the α-acylimine compound can be described as anα-acylimine compound product of contacting an α-diacyl compound with aprimary amine. Within this second α-acylimine compound description, asin the synthesis of the α-acylimine compound, the α-diacyl compound andthe primary amine are separate and independent elements. Thus, in thesecond α-acylimine compound description, the α-acylimine compound can befurther described using any combination of the α-diacyl compound elementdescribed herein and the primary amine element as described herein. Asnon-limiting examples, the α-acylimine compound can be the α-acyliminecompound product of contacting an α-diacyl compound with a primary aminecomprising an —NH₂ group and an organyl group; alternatively, contactingan α-diacyl compound with a primary amine comprising an —NH₂ group and ametal salt complexing group; alternatively, contacting an α-diacylcompound with a primary amine comprising an —NH₂ group, a metal saltcomplexing group, and a linking group linking the metal salt complexinggroup to the —NH₂ group; alternatively, contacting an α-diacyl compoundwith a primary amine comprising an —NH₂ group and an organyl groupconsisting of inert functional groups; alternatively, contacting anα-diacyl compound with a primary amine comprising an —NH₂ group and ahydrocarbyl group; alternatively, contacting an α-diacyl compound with aprimary amine consisting of an —NH₂ group and an organyl group;alternatively, contacting an α-diacyl compound with a primary aminesconsisting of an —NH₂ group, a metal salt complexing group, and alinking group linking the metal salt complexing group to the —NH₂ group;alternatively, contacting an α-diacyl compound with a primary amineconsisting of an —NH₂ group and an organyl group consisting of inertfunctional groups; or alternatively, contacting an α-diacyl compoundwith a primary amine consisting of an —NH₂ group and a hydrocarbylgroup. The α-acylimine compound can be further described using anycombination of the α-diacyl compound element described herein and theprimary amine element as described herein.

In a third description, the α-acylimine compounds can be described as anα-acylimine compound product produced by any process as described hereinand can be further described using any embodiments of the processes asdescribed herein.

In a fourth description, the α-acylimine compound can be described ashaving any structure as indicated in Table 4. In some embodiments, theα-acylimine compound can have Structure 1b or Structure 27b;alternatively, Structure 2b or Structure 28b; alternatively, Structure3b, Structure 4b, Structure 5b, Structure 29b, Structure 30b, orStructure 31b; alternatively, Structure 6b or Structure 32b;alternatively, Structure 7b, Structure 8b, mixtures of Structure 9b andStructure 10b, Structure 33b, Structure 34b, or mixtures of Structure35b and Structure 36b; alternatively, Structure 11b, Structure 12b,Structure 13b, Structure 37b, Structure 38b, or Structure 39b; oralternatively, Structure 11b or Structure 37b. In other embodiments, theα-acylimine compound can have Structure 27b; alternatively, Structure28b; alternatively, Structure 29b, Structure 30b, or Structure 31b;alternatively, Structure 32b; alternatively, Structure 33b, Structure34b, or mixtures of Structure 35b and Structure 36b; alternatively,Structure 37b, Structure 38b, or Structure 39b; or alternatively,Structure 37b. In yet other embodiments, the α-acylimine compound canhave Structure 14b; alternatively, Structure 15b; alternatively,Structure 16b, Structure 17b, or Structure 18b; alternatively, Structure19b; alternatively, Structure 20b, Structure 21b, or mixtures ofStructure 22b and Structure 23b; alternatively, Structure 24b, Structure25b, or Structure 26b; or alternatively, Structure 24b. TABLE 4 Exampleα-Acylimine Compounds

The α-acylimine compounds of Table 4 can be prepared utilizing variousmethods as described herein. Depending upon the α-acylimine compoundpreparation method, the α-diacyl compound and the primary amine can beseparate and independent elements in the preparation of the α-acyliminecompound. Therefore, the R^(x)s of α-diacyl compound having Structures1-12 (Table 1), the R^(ax)s of the primary amines having Structures1a-4a, the linking groups 1L-5L (Table 3) of the primary amine havingStructure 5a, and the metal salt complexing group R^(cx)s havingStructures 1c-22c (Table 2) of the primary amine having Structure 5a areseparate and independent elements of the α-acylimine compounds of Table4. Thus, the α-acylimine compounds of Table 4 can be further describedusing any combination of the R^(x)s of α-diacyl compound havingStructures 1-12 (Table 1) as described herein, the R^(ax)s of theprimary amines having Structures 1a-4a as described herein, the linkinggroups 1L-5L (Table 3) of the primary amine having Structure 5a asdescribed herein, and the metal salt complexing group R^(cx)s havingStructures 1c-22c (Table 2) of the primary amine having Structure 5a asdescribed herein.

Metal Salts

The metal salts, M-X_(p), employed in forming the α-acylimine orα-diimine metal complexes can be any salt comprising any metal atom.Suitable metal salts can comprise any metal from groups IVB through VIIIof the CAS version of the periodic table of elements. In someembodiments, the metal salt can be titanium, zirconium, hafnium,vanadium, niobium, tantalum, chromium, manganese, iron, cobalt, nickel,palladium, platinum, or mixtures thereof. In other embodiments, themetal salt can comprise chromium, iron, cobalt, nickel, palladium, ormixtures thereof; alternatively, chromium, iron, cobalt, or mixturesthereof; alternatively, iron, cobalt, or mixtures thereof;alternatively, nickel, palladium, or mixtures thereof; alternatively,chromium; alternatively, iron; alternatively, cobalt; alternatively,nickel; or alternatively, palladium.

In some embodiments, the metal salt is dicoordinating; can complex withtwo complexing atoms (e.g. the two imine nitrogen atoms of an α-diiminecompound or the oxygen atom of the acyl group and the nitrogen atom ofthe imine group of an α-acylimine compound). In other embodiments, themetal salt can be tricoordinating; can complex with three complexingatoms (e.g. the two imine nitrogen atoms and heteroatom of the metalsalt complexing group of an α-diimine compound). Typically,dicoordinating metal salts are utilized with bidentate α-diiminecompounds and tricoordinating metal salts are utilized with tridentateα-diimine compounds.

In some embodiments wherein the α-diimine compound portion of theα-diimine metal complex is tridentate (e.g. the α-diimine compoundportion of the α-diimine metal complex comprises an α-diimine group anda metal salt complexing group), the metal salt can comprise chromium,iron, cobalt, or mixtures thereof; alternatively, iron, cobalt, ormixtures thereof; alternatively, iron; or alternatively, cobalt. In someembodiments wherein the α-diimine compound portion of the α-diiminemetal complex is bidentate (e.g. the α-diimine compound portion of theα-diimine metal complex comprises an α-diimine group and does notcontain a metal salt complexing group), the metal salt can comprisenickel, palladium, or mixtures thereof; alternatively, nickel, oralternatively, palladium.

The anion X, of the metal salt can be any anion. In some embodiments,the anion X can be a halide, carboxylate, acetonate, alkoxide,phenoxide, nitrate, sulfate, phosphate, or chlorate. In someembodiments, the anion, X, is a halide or acetonate. In embodiments, thehalide can be fluorine, chlorine, bromine, iodine, or combinationsthereof; alternatively, chlorine, bromine, iodine, or combinationsthereof; alternatively, chlorine; alternatively, bromine, oralternatively, iodine. In carboxylate, acetonate, alkoxide or phenoxideembodiments, the carboxylate, acetonate, alkoxide, or phenoxide can beany C₁ to C₂₀ carboxylate, acetonate, alkoxide, or phenoxide; oralternatively, any C₁ to C₁₀ carboxylate, acetonate, alkoxide, orphenoxide. In some embodiments, the anion, X, can be a C₁ to C₁₀acetonate; alternatively, a C₁ to C₁₀ carboxylate; alternatively, a C₁to C₁₀ alkoxide; or alternatively, a C₁ to C₁₀ phenoxide. In otherembodiments, the anion X, can be acetylacetonate; alternatively,acetate; alternatively, 2-ethylhexanoate; or alternatively, triflate.

Generally, the number, p, of anions, X, is such that the total number ofnegative charges on the total number of X anions equals the oxidationstate of M. In some embodiments, p is 1, 2, or 3, and the total numberof negative charges on X is equal to the oxidation state of M. In otherembodiments, the total number of anions, p, is 2; or alternatively, 3.

In embodiments, tricoordinating metal salts can be chromium(II)chloride, chromium(III) chloride, chromium(II) fluoride, chromium(III)fluoride, chromium (II) bromide, chromium(III) bromide, chromium(II)iodide, chromium(III) iodide, chromium(II) acetate, chromium (III)acetate, chromium(III) acetylacetonate, chromium(II) 2-ethylhexanoate,chromium (II) triflate, chromium(III) nitrate, iron(II) chloride,iron(III) chloride, iron(II) fluoride, iron(III) fluoride, iron (II)bromide, iron(III) bromide, iron(II) iodide, iron(III) iodide, iron(II)acetate, iron (III) acetate, iron(II) acetylacetonate, iron(III)acetylacetonate, iron(II) 2-ethylhexanoate, iron (II) triflate,iron(III) nitrate, cobalt(II) chloride, cobalt(III) chloride, cobalt(II)fluoride, cobalt(III) fluoride, cobalt (II) bromide, cobalt(III)bromide, cobalt(II) iodide, cobalt(III) iodide, cobalt(II) acetate,cobalt (III) acetate, cobalt(II) acetylacetonate, cobalt(II)benzoylacetonate, cobalt(III) acetylacetonate, cobalt(II)2-ethylhexanoate, cobalt (II) triflate, cobalt(III) nitrate, vanadium(III) chloride, vanadium (II) chloride, vanadium(III) chloridetetrahydrofuran complex, vanadium (III) iodide, manganese(II) acetate,manganese(II) acetylacetonate, manganese(II) bromide, manganese(II)chloride, manganese(II) fluoride, manganese(III) fluoride, ormanganese(II) iodide. In some embodiments, the tricoordinating metalsalt can be chromium(II) chloride, chromium(III) chloride, chromium(II)acetate, chromium (III) acetate, chromium(III) acetylacetonate, iron(II)chloride, iron(III) chloride, iron(II) acetate, iron (III) acetate,iron(II) acetylacetonate, iron(III) acetylacetonate, cobalt(II)chloride, cobalt(III) chloride, cobalt(II) acetate, cobalt (III)acetate, or cobalt(II) acetylacetonate. In other embodiments, thetricoordinating metal salt metal salt can be chromium(II) chloride,chromium(III) acetylacetonate, iron(II) chloride, iron(II)acetylacetonate, iron(III) acetylacetonate, cobalt(II) chloride,cobalt(II) acetylacetonate. In other embodiments, the tricoordinatingmetal salt can be chromium(II) chloride; alternatively, chromium(III)acetylacetonate; alternatively, iron(II) chloride; alternatively,iron(II) acetylacetonate; alternatively, cobalt(II) chloride; oralternatively, cobalt(II) acetylacetonate.

In embodiments, dicoordinating metal salts can be nickel(II) chloride,nickel(II) fluoride, nickel (II) bromide, nickel(II) iodide, nickel(II)acetate, nickel(II) acetylacetonate, nickel(II) benzoylacetonate,nickel(II) 2-ethylhexanoate, nickel (II) triflate, nickel(II) nitrate,palladium(II) chloride, palladium(II) fluoride, palladium (II) bromide,palladium(II) iodide, palladium(II) acetate, palladium(II)acetylacetonate, or palladium(II) nitrate. In some embodiments, thedicoordinating metal salt can be nickel(II) chloride, nickel(II)acetylacetonate, palladium(II) chloride, or palladium(II)acetylacetonate. In other embodiments, the dicoordinating metal salt canbe alternatively, nickel(II) chloride; alternatively, nickel(II)acetylacetonate; alternatively, palladium(II) chloride; oralternatively, or palladium(II) acetylacetonate.

α-Acylimine Metal Complexes

The α-acylimine metal complexes can be described using any one ofseveral descriptions. While the α-acylimine metal complex descriptionsmay be indicated by labels such as first description, seconddescription, etc., these labels do not indicate a particular preferenceto the description of the α-acylimine metal complexes.

In a first description, the α-acylimine metal complex can be describedas a complex between an α-acylimine compound and a metal salt. Whilethis α-acylimine metal complex description appears to imply a specificα-acylimine metal complex synthesis method, this is not the intent. Themethod of preparing the α-acylimine metal complex is independent of themethod of describing the α-acylimine metal complex. Thus, while theα-acylimine metal complex can be described as a complex between anα-acylimine compound and a metal salt, the α-acylimine metal complex canbe prepared by contacting an α-acylimine compound and a metal salt orany other method described herein. The α-acylimine compound and themetal salt are separate and independent elements. Thus, the α-acyliminemetal complex can be further described using any combination of theα-acylimine compound element described herein and the metal salt elementas described herein.

In a second description, the α-acylimine metal complex can be describedas a product produced by any process described herein capable ofproducing the α-acylimine metal complex and can be further describedusing any embodiments of the processes described herein.

In a third description, the α-acylimine metal complex can have anystructure as indicated in Table 5. In some embodiments, the α-acyliminemetal complex can have Structure 1d or Structure 27d; alternatively,Structure 2d or Structure 28d; alternatively, Structure 3d, Structure4d, Structure 5d, Structure 29d, Structure 30d, or Structure 31d;alternatively, Structure 6d or Structure 32d; alternatively, Structure7d, Structure 8d, mixtures of Structure 9d and Structure 10d, Structure33d, Structure 34d, or mixtures of Structure 35d and Structure 36d;alternatively, Structure 11d, Structure 12d, Structure 13d, Structure37d, Structure 38d, or Structure 39d; or alternatively, Structure 11d orStructure 37d. In other embodiments, the α-acylimine metal complex canhave Structure 27d; alternatively, Structure 28d; alternatively,Structure 29d, Structure 30d, or Structure 31d; alternatively, Structure32d; alternatively, Structure 33d, Structure 34d, or mixtures ofStructure 35d and Structure 36d; alternatively, Structure 37d, Structure38d, or Structure 39d; or alternatively, Structure 37d. In yet otherembodiments, the α-acylimine metal complex can have Structure 14d;alternatively, Structure 15d; alternatively, Structure 16d, Structure17d, or Structure 18d; alternatively, Structure 19d; alternatively,Structure 20d, Structure 21d, or mixtures of Structure 22d and Structure23d; alternatively, Structure 24d, Structure 25d, or Structure 26d; oralternatively, Structure 24d. TABLE 5 Example α-Acylimine MetalComplexes

The α-acylimine metal complexes of Table 5 can be prepared utilizingvarious methods as described herein. Depending upon the α-acyliminemetal complex preparation method, the α-diacyl compound, the primaryamine, the metal salt, and/or the α-acylimine compound can each beseparate and independent elements in the preparation of the α-acyliminemetal complex. Therefore, the R^(x)s of α-diacyl compounds havingStructures 1-12 (Table 1), the metal salts, the R^(ax)s of the primaryamines having Structures 1a-4a, the linking groups 1L-5L (Table 3) ofthe primary amine having Structure 5a, and the metal salt complexinggroup R^(cx)s having Structures 1c-22c (Table 2) of the primary aminehaving Structure 5a are separate and independent elements of theα-acylimine metal complexes of Table 5. Thus, the α-acylimine metalcomplexes of Table 5 can be further described using any combination ofthe R^(x)s of α-diacyl compounds having Structures 1-12 (Table 1) asdescribed herein, the metal salts as described herein, the R^(ax)s ofthe primary amines having Structures 1a-4a as described herein, thelinking groups 1L-5L (Table 3) of the primary amine having Structure 5aas described herein, and the metal salt complexing group R^(cx)s havingStructures 1c-22c (Table 2) of the primary amine having Structure 5a asdescribed herein.

α-Diimine Metal Complexes

One aspect of the invention involves α-diimine metal complexes. Theα-diimine metal complexes can be described using any one of severaldescriptions. White the α-diimine metal complex descriptions may beindicated by labels such as first description, second description, etc.,these labels do not indicate a particular preference to the descriptionsof the α-diimine metal complexes.

In a first description, the α-diimine metal complex can be described asa metal salt complexed to an α-diimine compound or as a complex betweena diimine compound and a metal salt, the α-diimine compounds. Whitethese particular α-diimine metal complex descriptions appear to imply aspecific α-diimine metal complex preparation method, this is not theintent of α-diimine metal complex description. The method of preparingthe α-diimine metal complex is independent of the method of describingthe α-diimine metal complex. Thus, while the α-diimine metal complex maybe described as a complex between an α-diimine compound and a metalsalt, the α-diimine metal complex may be prepared by contacting anα-diimine compound and a metal salt, by contacting an α-acyliminecompound, an amine and a metal salt, or any other method describedherein. The α-diimine compounds and metal salts are separate andindependent elements of the α-diimine metal complex. Thus within thefirst α-diimine metal complex description, the α-diimine metal complexcan be described using any combination of α-diimine compound asdescribed herein and the metal salt as described herein.

In embodiments, the α-diimine metal complex can be described as adicoordinate metal salt complexed to a bidentate α-diimine compound. Insome embodiments, the α-diimine metal complex can be described as atricoordinate metal salt complexed to a tridentate α-diimine compound.It should be noted that while the later embodiment describes theα-diimine metal complex as a tricoordinate metal salt complexed to atridentate α-diimine compound, this description does not necessarilyimply that the three ligands of the tridentate α-diimine compound arecomplexed to the metal salt. For example, in example 7 a tricoordinatemetal salt is complexed to a tridentate α-diimine compound wherein themetal salt complexing group is not complexed to the metal salt and canbe utilized within other aspects of the invention as described herein.

In a second description, the α-diimine metal complex can be described asa product produced by any process described herein capable of producingthe α-diimine metal complex and may be further described using anyembodiments of the processes described herein.

In a third description, the α-diimine metal complex can be described ashaving any structure as indicated in Table 6. In embodiments, theα-diimine metal complex can have Structure 1e; alternatively, Structure2e; alternatively, Structure 3e, Structure 4e, or Structure 5e;alternatively, Structure 6e; alternatively, Structure 7e, Structure 8e,or mixtures of Structure 9e and Structure 10e; alternatively, Structure11e, Structure 12e, or Structure 13e; or alternatively, Structure 11e.In some embodiments, R^(a1) and R^(a1′) of Structures 1e-13e aredifferent (not identical). In some embodiments, R^(a1) of Structures 1eto/through 13e can have Structure 1g (derived from a primary aminehaving Structure 3a).

In other embodiments, R^(a1′) of Structures 1e to/through 13e can haveStructure 2g (derived from a primary amine having Structure 4a).

In other embodiments, R^(a1) of Structures 1e to/through 13e can haveStructure 1g and R^(a1′) of Structure 1e to/through 13e can haveStructure 2g. In some embodiments, wherein R^(a1) and R^(a1′) ofStructures 1e to/through 13e can have Structure 1g and Structure 2g,respectively, wherein Structure 1g and Structure 2g are different (notidentical).

In some embodiments, the α-diimine metal complex can have Structure 14eor Structure 27e; alternatively, Structure 15e or Structure 28e;alternatively, Structure 16e, Structure 17e, Structure 18e, Structure29e, Structure 30e, or Structure 31e; alternatively, Structure 19e orStructure 32e; alternatively, Structure 20e, Structure 21e, mixtures ofStructure 22e and Structure 23e, Structure 33e, Structure 34e, ormixtures of Structure 35e and Structure 36e; alternatively, Structure24e, Structure 25e, Structure 26e, Structure 37e, Structure 38e, orStructure 39e; or alternatively, Structure 24e or Structure 37e. Inother embodiments, the α-acylimine compound can have Structure 14e;alternatively, Structure 15e; alternatively, Structure 16e, Structure17e, or Structure 18e; alternatively, Structure 19e; alternatively,Structure 20e, Structure 21e, or mixtures of Structure 22e and Structure23e; alternatively, Structure 24e, Structure 25e, or Structure 26e; oralternatively, Structure 24e. In yet other embodiments, the α-acyliminecompound can have Structure 27e; alternatively, Structure 28e;alternatively, Structure 29e, Structure 30e, or Structure 31e;alternatively, Structure 32e; alternatively, Structure 33e, Structure34e, or mixtures of Structure 35e and Structure 36e; alternatively,Structure 37e, Structure 38e, or Structure 39e; or alternatively,Structure 37e. TABLE 6 Example α-Diimine Metal Complexes

The α-diimine metal complexes of Table 6 can be prepared utilizingvarious methods as described herein. Depending upon the α-diimine metalcomplex preparation method the α-diacyl compound, the two primaryamines, the metal salt, the α-acylimine compounds, and/or theα-acylimine metal complexes can each be separate and independentelements in the preparation of the α-diimine metal complex. Therefore,the R^(x)s of α-diacyl compounds having Structures 1-12 (Table 1), themetal salts, the R^(ax)s of the primary amines having Structures 1a-4a,the linking groups 1L-5L (Table 3) of the primary amine having Structure5a, and the metal salt complexing group R^(cx)s having Structures 1c-22c(Table 2) of the primary amine having Structure 5a are separate andindependent elements of the α-diimine metal complexes of Table 6. Thus,the α-diimine metal complexes of Table 6 can be further described usingany combination of the R^(x)s of α-diacyl compound having Structures1-12 (Table 1) as described herein, the metal salts as described herein,the R^(ax)s of the primary amines having Structures 1a-4a as describedherein, the linking groups 1L-5L (Table 3) of the primary amine havingStructure 5a as described herein, and the metal salt complexing groupR^(cx)s having Structures 1c-22c (Table 2) of the primary amine havingStructure 5a as described herein.

One skilled in the art will recognize that α-diimine metal complexStructures 14e though 39e formally show a monomeric form of atricoordinate metal salt complexed to a tridentate α-diimine compound.However, it should be noted that these structures do not necessarilyimply that dimeric forms of Structures having bridging X_(p) groups arenot formed. Additionally, it should also be noted that while α-diiminemetal complex Structures 14e though 39e, and other Structures disclosedherein, indicate that the two imine nitrogen and the metal saltcomplexing group form a dative bond with the metal atom, thesestructures do not necessarily imply that the three ligands of thetridentate α-diimine compound are complexed to the metal salt. Forexample, in example 7 a tricoordinate metal salt is complexed to atridentate α-diimine compound to form an α-diimine metal complexisolated in a dimeric form and the metal salt complexing group is notcomplexed to the metal salt. The examples further illustrate that thisα-diimine metal complex of example 7 can be utilized within otheraspects of the invention as described herein. Provided the teachings ofthe present disclosure, the skilled artisan may also recognize that theα-diimine metal complex Structures herein do not show the presence ofany complexing solvent molecules and may appreciate that depending uponthe solvent(s) used in the preparation of α-diimine metal complexStructures 1e though 39e, and other Structures disclosed herein, theα-diimine metal complexes can be isolated in forms having complexedsolvent atoms, (e.g. THF, acetonitrile).

α-Diimine Compounds

The α-diimine compounds can be described using any one of severaldescriptions. While these descriptions may be indicated by labels suchfirst description, second description, etc., these labels do notindicate a preference towards a particular description of the α-diiminecompounds.

In a first description, the α-diimine compound can be minimallydescribed as a compound comprising an α-diimine group. In embodiments,the α-diimine compound can be described as a compound comprising 1) anα-diimine group and 2) two α-diimine nitrogen groups. In this firstα-diimine compound description, the α-acylimine group can be furtherdescribed as being derived from an α-diacyl compound. Thus,alternatively, the α-acylimine compound can be described as compoundcomprising 1) an α-diimine group derived from an α-diacyl compound and2) two α-diimine nitrogen groups; or alternatively, as compoundconsisting of 1) an α-diimine group derived from an α-diacyl compoundand 2) two α-diimine nitrogen group. In the first α-diimine compounddescription, the α-diacyl compound, and each of the two α-diiminenitrogen groups are separate and independent elements of the α-diiminecompound description. Thus, within the first α-diimine compounddescription, the α-diimine compound can have any combination of theα-diacyl compound as described herein and the α-diimine nitrogen groupsas described herein.

In the first α-diimine compound description, the α-diacyl compound fromwhich the α-diimine compound is derived can be any α-diacyl compounddescribed herein. In embodiments, the two α-diimine nitrogen groups caneach independently comprise an organyl group; alternatively, comprise ametal salt complexing group; alternatively, comprise a metal saltcomplexing group and a linking group linking the metal salt complexinggroup to the α-diimine nitrogen group nitrogen atom; alternatively,comprise an organyl group consisting of inert functional groups;alternatively, comprise a hydrocarbyl group; alternatively, consist ofan organyl group; alternatively, consist of a metal salt complexinggroup and a linking group linking the metal salt complexing group to theα-diimine nitrogen group nitrogen atom; alternatively, consist of anorganyl group consisting of inert functional groups; or alternatively,consist of a hydrocarbyl group.

In some embodiments, the two α-diimine nitrogen groups can be the same.In other embodiments, the two α-diimine nitrogen groups can bedifferent. In particular embodiments, the two α-diimine nitrogen groupscomprise two different organyl groups; alternatively, comprise twodifferent organyl groups consisting of inert functional groups;alternatively, comprise two different hydrocarbyl groups; alternatively,consist of two different organyl groups; alternatively, consist of twodifferent organyl groups consisting of inert functional groups; oralternatively, consist of two different hydrocarbyl groups. In someother particular embodiments, the first α-diimine nitrogen groupcomprises an organyl group consisting of inert functional groups and thesecond α-diimine nitrogen group comprises a metal salt complexing group;alternatively, the first α-diimine nitrogen group comprises an organylgroup consisting of inert functional groups and the second α-diiminenitrogen group comprises a metal salt complexing group and a linkinggroup linking the metal salt complexing group to second α-diiminenitrogen group nitrogen atom; alternatively, the first α-diiminenitrogen group comprises a hydrocarbyl group and the second α-diiminenitrogen group comprises a metal salt complexing group; alternatively,the first α-diimine nitrogen group comprises a hydrocarbyl group and thesecond α-diimine nitrogen group comprises a metal salt complexing groupand a linking group linking the metal salt complexing group to thesecond α-diimine nitrogen group nitrogen atom; alternatively, the firstα-diimine nitrogen group consists of an organyl group consisting ofinert functional groups and the second α-diimine nitrogen group consistsof a metal salt complexing group and a linking group linking the metalsalt complexing group to the second α-diimine nitrogen group nitrogenatom ; or alternatively, the first α-diimine nitrogen group consists ofa hydrocarbyl group and the second α-diimine nitrogen group consists ofa metal salt complexing group and a linking group linking the metal saltcomplexing group to the second α-diimine nitrogen group nitrogen atom.

As the primary amine —NH₂ group becomes the α-diimine group's nitrogenatom, the organyl group, metal salt complexing group, linking group,organyl group consisting of inert functional groups, or hydrocarbylgroups of the primary amine becomes an α-diimine nitrogen group. Thus,the α-diimine nitrogen groups can have the same embodiments as theorganyl group, metal salt complexing group, linking group, organyl groupconsisting of inert functional groups, and hydrocarbyl groups of theprimary amine as described herein. Therefore, the organyl group, metalsalt complexing group, linking group, organyl group consisting of inertfunctional groups, and hydrocarbyl groups of the primary aminesembodiment described herein are generally applicable to the descriptionof the α-acylimine compound with the proviso that the linking grouplinks the metal salt complexing group to the imine nitrogen atom of theα-acylimine group instead of the —NH₂ group of the primary amine.

In a second description, the α-diimine compound can be described as anα-diimine compound product of contacting an α-diacyl compound with twoprimary amines. While this particular α-diimine compound descriptionappears to imply a specific α-diimine compound synthesis method, this isnot the intent of α-diimine compound. The method of preparing theα-diimine compound is independent of the description of the α-diiminemetal complex. Thus, while the α-diimine compound can be described as anα-diimine compound product of contacting an α-diacyl compound with twoprimary amines, the α-diimine compound can be prepared by using anymethod described herein. In the second α-diimine compound descriptionthe α-diacyl compound and each of the two primary amines are separateand independent elements of the α-diimine compound description. Thus,within the second α-diimine compound description, the α-diimine compoundcan have any combination of the α-diacyl compound as described hereinand two primary amines as described herein.

In the second α-diimine compound description, the α-diacyl compound canbe any α-diacyl compound described herein. In an aspect, the two primaryamines are the same. In some embodiments, the two primary amines aredifferent. In embodiments, at least one of the primary amines consistsof an —NH₂ group and a hydrocarbyl group or consists of an —NH₂ groupand an organyl group consisting of inert functional groups. Inparticular embodiments, the α-diimine compound is a product of reactingan α-diacyl compound with two different the two primary aminescomprising an —NH₂ group and an organyl groups; alternatively,comprising an —NH₂ group and an organyl groups consisting of inertfunctional groups; alternatively, comprising an —NH₂ group and ahydrocarbyl group; alternatively, consisting of an —NH₂ group and anorganyl groups; alternatively, consisting of an —NH₂ group and anorganyl group consisting of inert functional groups; or alternatively,consisting of an —NH₂ group and a hydrocarbyl group.

In embodiments, the α-diimine compound is a product of reacting α-diacylcompound with two different primary amines. In particular embodiments,the α-diimine compound is a product of reacting α-diacyl compound withtwo different primary amines, wherein the first primary amine comprisesan —NH₂ group and an organyl group consisting of inert functional groupsand the second primary amine comprises an —NH₂ group and a metal saltcomplexing group; alternatively, the first primary amine comprises an—NH₂ group and an organyl group consisting of inert functional groupsand the second primary amine comprises an —NH₂ group, a metal saltcomplexing group, and a linking group linking the metal salt complexinggroup the —NH₂ group; alternatively, the first primary amine comprisesan —NH₂ group and a hydrocarbyl group and the second primary aminecomprises an —NH₂ group and a metal salt complexing group;alternatively, the first primary amine comprises an —NH₂ group and ahydrocarbyl group and the second primary amine comprises an —NH₂ group,a metal salt complexing group, and a linking group linking the metalsalt complexing group to the —NH₂ group; alternatively, the firstprimary amine consists of an —NH₂ group and an organyl group consistingof inert functional groups and the second primary amine consists of an—NH₂ group, a metal salt complexing group, and a linking group linkingthe metal salt complexing group to the —NH₂ group; or alternatively, thefirst primary amine consists of an —NH₂ group and a hydrocarbyl groupand the second primary amine consists of an —NH₂ group, a metal saltcomplexing group, and a linking group linking the metal salt complexinggroup to the —NH₂ group.

In a third description, the α-diimine compounds can be described as aproduct produced by any process described herein capable of producingthe α-diimine compounds and may be further described using anyembodiments of the processes described herein.

In a fourth description, the α-diimine compound can be described ashaving any a structure as indicated in Table 7. In embodiments, theα-diimine compound can have Structure 1f; alternatively, Structure 2f;alternatively, Structure 3f, Structure 4f, or Structure 5f;alternatively, Structure 6f; alternatively, Structure 7f, Structure 8f,or mixtures of Structure 9f and Structure 10f; alternatively, Structure11f, Structure 12f, or Structure 13f; or alternatively, Structure 11f.In some embodiments, R^(a1) and R^(a1′) of Structures 1f-13f aredifferent (not identical). In some embodiments, R^(a1) of Structures1f-13f can have Structure 1g (derived from a primary amine havingStructure 3a). In other embodiments, R^(a1′) of Structures 1f-13f canhave Structure 1g can have Structure 2g (derived from a primary aminehaving Structure 4a). In other embodiments, Ra1 of Structures 1f-13f canhave Structure 1g and R^(a1′) of Structures 1f-13f can have Structure2g. In yet other embodiments, wherein R^(a1) and R^(a1′) of Structures1f-13f can have Structure 1g and Structure 2g, respectively, Structure1g and Structure 2g are different (not identical).

In some embodiments, the α-diimine compound can have Structure 14f orStructure 27f; alternatively, Structure 15f or Structure 28f;alternatively, Structure 16f, Structure 17f, Structure 18f, Structure29f, Structure 30f, or Structure 31f; alternatively, Structure 19f orStructure 32f; alternatively, Structure 20f, Structure 21f, mixtures ofStructure 22f and Structure 23f, Structure 33f, Structure 34f, ormixtures of Structure 35f and Structure 36f, alternatively, Structure24f, Structure 25f, Structure 26f, Structure 37f, Structure 38f, orStructure 39f, or alternatively, Structure 24f or Structure 37f. Inother embodiments, the α-diimine compound can have Structure 14f;alternatively, Structure 15f; alternatively, Structure 16f, Structure17f, or Structure 18f; alternatively, Structure 19f; alternatively,Structure 20f, Structure 21f, or mixtures of Structure 22f and Structure23f; alternatively, Structure 24f, Structure 25f, or Structure 26f, oralternatively, Structure 24f. In yet other embodiments, the α-diiminecompound can have Structure 27f; alternatively, Structure 28f;alternatively, Structure 29f, Structure 30f, or Structure 31f;alternatively, Structure 32f; alternatively, Structure 33f, Structure34f, or mixtures of Structure 35f and Structure 36f; alternatively,Structure 37f, Structure 38f, or Structure 39f; or alternatively,Structure 37f. TABLE 7 Example α-Diimine Compounds

Ideally, the α-diimine compounds of Table 7 could be prepared from anα-diacyl compound and two primary amines which are separate andindependent elements. Thus, the R^(x)s of α-diacyl compound havingStructures 1-12 (Table 1), the R^(ax)s of the primary amines havingStructures 1a-4a, the linking groups 1L-5L (Table 3) of the primaryamine having Structure 5a, and the metal salt complexing group R^(cx)shaving Structures 1c-22c (Table 2) of the primary amine having Structure5a are separate and independent elements of the α-diimine compounds ofTable 7. Thus, the α-diimine compounds of Table 7 can be furtherdescribed using any combination of the R^(x)s of α-diacyl compoundshaving Structures 1-12 (Table 1) as described herein, the R^(ax)s of theprimary amines having Structures 1a-4a as described herein, the linkinggroups 1L-5L (Table 3) of the primary amine having Structure 5a asdescribed herein, and the metal salt complexing group R^(cx)s havingStructures 1c-22c (Table 2) of the primary amine having Structure 5a asdescribed herein.

General Metal Complex and Intermediate Synthesis Methods

An aspect of the invention relates to methods of preparing α-diiminemetal complexes. As described herein, production of particular α-diiminemetal complexes can motivate selection of particular starting materials,(e.g. α-diacyl compounds, primary amines, and metal salts),intermediates (e.g. α-acylimine compounds and α-acylimine metalcomplexes), and α-diimine metal complexes.

The methods for producing an α-diimine metal complex generally compriseforming at least one imine bond in the presence of a metal salt, a metalcomplex, or combinations thereof and recovering an α-diimine metalcomplex. In some embodiments, the method for producing an α-diiminemetal complex comprises forming at least one imine bond in the presenceof a metal salt, α-acylimine metal complex, or combinations thereof andrecovering an α-diimine metal complex. In some embodiments, the methodfor producing an α-diimine metal complex comprises forming at least oneimine bond in the presence of a metal salt. In further embodiments, themethod for producing an α-diimine metal complex comprises forming atleast one imine bond in the presence of an α-acylimine metal complex.Within these methods, the metal salt or α-acylimine metal complex, theα-diimine metal complex formed, and the specific imine bond or iminebonds formed, are separate and independent elements. Given the teachingsprovided, the skilled artisan can recognize which combination ofingredients may lead to a desired α-diimine metal complex that includesthe desired elements. The combinations of compounds that can be used toproduce a particular α-diimine metal complex utilizing the synthesismethods are described herein.

The α-diacyl compounds, primary amines, and metal salts are separate andindependent elements in the preparation of the α-diimine metalcomplexes. Additionally, the intermediate α-acylimine compounds and/orthe α-acylimine metal complexes can be separate and independent elementsof the α-diimine metal complex preparation methods. Thus, the α-diiminemetal complex preparation methods can use any combination of theα-diacyl compounds described herein, primary amines described herein,metal salts described herein, α-acylimine compounds described herein,and α-acylimine metal complexes described herein to produce the desiredα-diimine metal complexes utilizing the herein described preparationmethods. Provided the teachings of the present disclosure, a skilledartisan should recognize how combinations of ingredients may be variedin order to produce a desired metal complex including the desiredelements and their variations.

Methods for Preparing α-Acylimine Compounds

The method of preparing an α-acylimine compound comprises contacting anα-diacyl compound and a primary amine. In some embodiments, theα-acylimine compound is recovered. In other embodiments, the α-acyliminecompound can be purified using methods known to those skilled in theart, such as recrystallization. In yet other embodiments, theα-acylimine compound is used as is, e.g., as an unpurified reactionproduct.

Within the α-acylimine compound production method the primary amine andthe α-diacyl compound are separate and independent elements. Thus,α-acylimine compound can be prepared using any combination of theprimary amine as described herein and the α-diacyl compound as describedherein. In some embodiments, the primary amine can be a mixture ofsimilar primary amines, e.g. a mixture of primary amines consisting ofan —NH₂ group and hydrocarbyl group, a mixture of primary aminesconsisting of an —NH₂ group and an organyl group consisting of inertfunctional groups, or a mixture of primary amines comprising an —NH₂group and a metal salt complexing group. In additional embodiments, theα-diacyl compound can be a mixture of α-diacyl compounds.

Solvents and catalysts that can be utilized within the α-acyliminecompound synthesis methods are described herein and are generallyapplicable to methods of producing α-acylimine compounds. Productionconditions such as reagent molar ratios, temperatures, pressure, andcontact times, among others, are also described herein and are generallyapplicable to methods of producing α-acylimine compounds.

Methods for Preparing α-Acylimine Metal Complexes

Various synthesis paths can be employed to produce the α-acylimine metalcomplexes. Described herein are several preparation methods that can beutilized. While the α-acylimine metal complex preparation methods may bedesignated as ‘first method’, ‘second method’, etc . . . , thesedesignations do not imply any preference for a particular method ofpreparing the α-acylimine metal complexes.

In a first method, the method of preparing an α-acylimine metal complexcomprises contacting an α-acylimine compound with a metal salt. In someembodiments, the α-acylimine metal complex is recovered. In otherembodiments, the α-acylimine metal complex can be purified using methodsknown to those skilled in the art, such as recrystallization. In yetother embodiments, the α-acylimine metal complex can be used as is.

Within the first α-acylimine metal complex production method the metalsalt and α-acylimine compound are separate and independent elements.Thus, utilizing the first α-acylimine metal complex production methodthe α-acylimine metal complex can be prepared using any combination ofthe metal salt as described herein and the α-acylimine compound asdescribed herein. In some embodiments, the α-acylimine compound can be amixture of similar α-acylimine compounds, e.g. a mixture of α-acyliminecompounds produced by contacting α-diacyl compound with a mixture ofprimary amines consisting of an —NH₂ group and a hydrocarbyl group, amixture of α-acylimine compounds produced by contacting α-diacylcompound with a mixture of primary amines consisting of an —NH₂ groupand an organyl group consisting of inert functional groups, or a mixtureof α-acylimine compounds produced by contacting an α-diacyl compoundwith a mixture of primary amines comprising an —NH₂ group and an metalsalt complexing group.

In a second method, the method for preparing an α-acylimine metalcomplex comprises contacting an α-diacyl compound, a metal salt, and aprimary amine. In some embodiments, an α-acylimine metal complex isrecovered. In other embodiments, the α-acylimine metal complex can bepurified using methods know to those skilled in the art, such asrecrystallization. In yet other embodiments, the α-acylimine metalcomplex can be used as is.

In a third method, the method to produce an α-acylimine metal complexcomprises a) contacting an α-diacyl compound and a primary amine to forma mixture containing an α-acylimine compound, and b) contacting a metalsalt with the mixture containing the α-acylimine compound. In someembodiments, an α-acylimine metal complex is recovered. In otherembodiments, the α-acylimine metal complex can be purified using methodsknown to those skilled in the art, such as recrystallization. In yetother embodiments, the α-acylimine metal complex is used as is.

Within the second and third α-acylimine metal complex productionmethods, the primary amine, the α-diacyl compound, and the metal saltare separate and independent elements. Thus utilizing the second andthird α-acylimine metal complex production methods, the α-acyliminemetal complex can be prepared utilizing any combination of the primaryamine as described herein, the α-diacyl compound as described herein,and the metal salt as described herein. Provided the teachings of thepresent disclosure, a skilled artisan can recognize how combinations ofingredients, e.g.—a primary amine, α-diacyl compound, and metal salt,may be varied in order to produce a desired metal complex includingthose ingredients and their variations. In some embodiments within thesecond and/or third α-acylimine metal complex production methods, theprimary amine can be a mixture of similar primary amines, e.g. a mixtureof primary amines consisting of an —NH₂ group and hydrocarbyl group, amixture of primary amines consisting of an —NH₂ group and an organylgroup consisting of inert functional groups, or a mixture of primaryamines comprising an —NH₂ group and a metal salt complexing group. Insome embodiments, within the second and third α-acylimine metal complexproduction methods, the α-diacyl compound can be a mixture of α-diacylcompounds.

Solvent and catalysts and solvents that can be utilized withinα-acylimine metal complex synthesis methods are described herein and aregenerally applicable to methods of producing α-acylimine metalcomplexes. Production conditions such as reagent molar ratios,temperatures, pressure, and contact times, among others, are alsodescribed herein and are generally applicable to methods of producingα-acylimine metal complexes.

Methods for Preparing α-Diimine Metal Complexes

Various synthesis paths can be employed to produce the α-diimine metalcomplexes by forming at least one imine bond in the presence of a metalsalt, α-acylimine metal complex, or combinations thereof. Describedherein are several methods that can be utilized. While methods may bedesignated as ‘first method’, ‘second method’, etc., these designationsdo not imply any preferences for particular method of preparingα-diimine metal complexes.

In a first method, the method to produce an α-diimine metal complex,comprises a) contacting an α-acylimine metal complex and a primary amineto form a mixture, and b) recovering the α-diimine metal complex fromthe mixture. In some embodiments, the α-diimine metal complex can bepurified using methods known to those skilled in the art, such asrecrystallization. In yet other embodiments, the α-acylimine metalcomplex can be used as is.

Within the first α-diimine metal complex production method, theα-acylimine metal complex and the primary amine are separate andindependent elements. Thus in the first α-diimine metal complexproduction method, the α-diimine metal complex can be prepared utilizingany combination of α-acylimine metal complex as described herein andprimary amine as described herein. In some particular embodiments, theprimary amine used to produce the α-acylimine compound of theα-acylimine metal complex and the primary amine contacted with theα-acylimine metal complex are different (not identical). For example, intwo non-limiting examples, the primary amine can comprise an —NH₂ groupand a metal salt complexing group and the α-acylimine metal complex cancomprise a complex between an α-acylimine compound and metal salt,wherein the α-acylimine compound comprises 1) an α-acylimine groupderived from an α-diacyl compound and 2) an imine nitrogen groupconsisting of a hydrocarbyl group; or the primary amine can consist ofan —NH₂ group and a hydrocarbyl group and the α-acylimine metal complexcan comprise a complex between an α-acylimine compound and metal saltwherein the α-acylimine compound comprises 1) an α-acylimine groupderived from an α-diacyl compound and 2) an imine nitrogen groupcomprising a metal salt complexing group. Provided the teachings of thepresent disclosure, the skilled artisan should recognize howcombinations of particular α-acylimine metal complexes and primaryamines can be varied in order to produce an α-acylimine metal complexthat includes the α-acylimine metal complex and primary amine selected.

In some embodiments, the primary amine can be a mixture of similarprimary amines, e.g. a mixture of primary amines consisting of an —NH₂group and hydrocarbyl group, a mixture of primary amines consisting ofan —NH₂ group and an organyl group consisting of inert functionalgroups, or a mixture of primary amines comprising an —NH₂ group and ametal salt complexing group. In some embodiments, the α-acylimine metalcomplex can be a mixture of similar α-acylimine metal complexes, e.g. amixture of α-acylimine compounds produced by contacting an α-diacylcompound with a mixture of primary amines consisting of an —NH₂ groupand a hydrocarbyl group, a mixture of α-acylimine compounds produced bycontacting an α-diacyl compound with a mixture of primary aminesconsisting of an —NH₂ group and an organyl group consisting of inertfunctional groups, or a mixture of α-acylimine compounds produced bycontacting an α-diacyl compound with a primary amine comprising an —NH₂group and an metal salt complexing group.

In a second method, the method to produce an α-diimine metal complexcomprises a) contacting an α-acylimine compound, a metal salt, and aprimary amine to form a mixture, and b) recovering the α-diimine metalcomplex from the mixture. In some embodiments, the α-diimine metalcomplex may be purified using methods known to those skilled in the art,such as recrystallization. In yet other embodiments, the α-acyliminemetal complex can be used as is, e.g., as an unpurified reactionproduct.

In a third method, the method to produce an α-diimine metal complexcomprises a) contacting an α-acylimine compound and a metal salt to forma mixture containing an α-acylimine metal complex b) contacting aprimary amine with the mixture containing an α-acylimine metal complexand c) recovering the α-diimine metal complex. In some embodiments, theα-diimine metal complex may be purified using methods known to thoseskilled in the art, such as recrystallization. In yet other embodiments,the α-acylimine metal complex can be used as is, e.g., as an unpurifiedreaction product.

Within the second and third α-diimine metal complex production methods,the α-acylimine compound, the metal salt, and the primary amine areseparate and independent elements. Thus within the second and thirdα-diimine metal complex production methods, the α-diimine metal complexcan be produced using any combination of the α-acylimine compound asdescribed herein, the metal salt as described herein, and the primaryamine as described herein. In some particular embodiments, the primaryamine used to produce the α-acylimine compound and the primary aminecontacted with the α-acylimine compound are different (not identical).For example, in two non-limiting examples, the primary amine used toproduce the o-acylimine compound can consist of an —NH₂ group and ahydrocarbyl group and the primary amine contacted with the α-acyliminecompound and metal salt or mixture containing an α-acylimine metalcomplex comprises an —NH₂ group and metal salt complexing group; or theprimary amine used to produce the α-acylimine compound consists of an—NH₂ group and a hydrocarbyl group and the primary amine contacted withthe α-acylimine compound and metal salt or mixture containing anα-acylimine metal complex consists of an —NH₂ group and hydrocarbylgroup different than the primary amine utilized to produce α-acyliminecompound. Provided the teachings of the present disclosure, the skilledartisan should recognize how combinations of particular α-acyliminecompounds, metal salts, and primary amines can be varied in order toproduce an α-acylimine metal complex including the α-acylimine compound,metal salt, and primary amine selected.

In some embodiments, the α-acylimine compound can be a mixture ofsimilar α-acylimine compounds, e.g. a mixture of α-acylimine compoundsproduced by contacting α-diacyl compound with a mixture of primary amineconsisting of an —NH₂ group and a hydrocarbyl group, a mixture ofα-acylimine compounds produced by contacting α-diacyl compound with amixture of primary amine consisting of an —NH₂ group and an organylgroup consisting of inert functional groups, or a mixture of α-acyliminecompounds produced by contacting an α-diacyl compound with a mixture ofprimary amine comprising an —NH₂ group and a metal salt complexinggroup. In other embodiments, the primary amine used in the synthesis ofthe α-diimine metal complex can be a mixture of similar primary amines,e.g. a mixture of primary amines consisting of an —NH₂ group andhydrocarbyl group, a mixture of primary amines consisting of an —NH₂group and an organyl group consisting of inert functional groups, or amixture of primary amines comprising an —NH₂ group and a metal saltcomplexing group.

In some particular embodiments, the primary amine utilized in the first,second, and third α-diimine metal complex production methods describedabove is a different primary amine than that utilized to produce theα-acylimine compound or α-acylimine metal complex. For example in twonon-limiting cases, if the primary amine used to produce α-acyliminecompound or α-acylimine metal complex comprises an —NH₂ group and anorganyl group then the primary amine contacted with the α-acyliminecompound or α-acylimine metal complex could be a different primary aminecomprising an —NH₂ group and an organyl group; or, if the primary amineused to produce α-acylimine compound or α-acylimine metal complexcomprises an —NH₂ group and an organyl group consisting of inertfunctional groups, then the primary amine contacted with the α-acyliminecompound or α-acylimine metal complex could be primary amines comprisingan —NH₂ group and a metal salt complexing group. One skilled in the artwill recognize that these are non-limiting examples and can envisionthat within these embodiments any combination of the two primary aminesas described herein can be utilized with the stipulation that the twoprimary amines are different.

In a fourth method, the method to produce the α-diimine metal complexcomprises a) contacting an α-diimine compound with a metal salt, and b)recovering the α-diimine metal salt. In further embodiments, theα-diimine metal complex is purified using methods known to those skilledin the art, such as recrystallization. Within the fourth α-diimine metalcomplex production method, the α-diimine compound and metal salt areseparate and independent elements. Thus, the α-diimine metal complex canbe produced utilizing any combination of the α-diimine compound asdescribed herein and the metal salt as described herein. Provided theteachings of the present disclosure, the skilled artisan shouldrecognize how combinations of α-diimine compound and metal salt may bevaried in order to produce a particular α-acylimine metal complexincluding the α-diimine compound and metal salt selected.

Applicable catalyst and solvent that can be utilized within theseα-diimine metal complex synthesis methods are described herein and aregenerally applicable to methods of producing α-diimine metal complexes.Production conditions such as molar ratios, temperatures, pressure, andcontact times, among others, are also described herein and are generallyapplicable to methods of producing α-diimine metal complexes.

The α-diimine metal complex synthesis method can also comprise any steprequired to produce the α-acylimine compounds and/or the α-acyliminemetal complexes utilized in the α-diimine metal complex syntheses. Assuch, the α-diimine metal complex synthesis can be described as processutilizing an α-diacyl compound, two primary amines, and a metal salt andhaving an α-acylimine compounds and/or α-acylimine metal complexes as anintermediate product which can be isolated and/or purified or used asis. Provided these α-diimine metal complex synthesis descriptions theskilled artisan may recognize that the two primary amines can be labeledfirst or second primary amine as needed to adequately describe theprocess. One skilled in the art provided these teachings may alsorecognize that even though the first, second, and third α-diimine metalcomplex synthesis steps are annotated with steps a), b), etc., theα-diimine metal complex synthesis steps can be re-annotated to provideconsistent step annotation to incorporate steps utilized in producingthe α-acylimine compounds and/or the α-acylimine metal complexes intothe α-diimine metal complex synthesis descriptions. Additionally, theact of incorporating the steps required to produce the α-acyliminecompounds and/or α-acylimine metal complexes into the methods ofproducing the α-diimine metal complexes can create a situation wherein asynthesis path may include more than one mixture In these scenarios,such mixtures can be prefaced with a descriptor such as first, second,etc., to provide unambiguous references to the mixtures within theα-diimine metal complex synthesis. Thus, in a non limiting example, aprocess to produce an α-acylimine metal complex from an α-diacylcompound, two primary amines, and a metal salt by putting together thevarious compound descriptions described herein can comprise the steps a)contacting an α-diacyl compound with a first primary amine to form afirst mixture containing an α-acylimine compound; b) contacting thefirst mixture with a metal salt to form a second mixture containing anα-acylimine metal complex, c) contacting a second primary amine with thesecond mixture to form an α-diimine metal complex, and d) recovering theα-diimine metal complex.

Reagent Molar Ratios, Solvents, Reaction Conditions and Metal Complexand Intermediate Yields

As described herein, an α-diimine metal complex may be produced viavarious synthesis paths. Molar ratios of reagents employed in thevarious synthesis paths are indicated herein and can be generallyapplied to the methods of producing the α-diimine metal complex asdescribed herein.

Generally, whenever a primary amine is contacted with an α-diacylcompound, e.g. to form an α-acylimine compound or an α-acylimine metalcomplex, the molar ratio of primary amine to α-diacyl compound can beany molar ratio capable of producing the α-acylimine compound orα-acylimine metal complex. In some embodiments, the molar ratio ofprimary amine to α-diacyl compound can be less than 1.1:1;alternatively, less than 1.05:1; alternatively, less than 1.02:1; oralternatively, less than 1:1. In other embodiments, the molar ratio ofprimary amine to α-diacyl compound can range from 0.75:1 to 1.1:1;alternatively, range from 0.85:1 to 1.05:1; or alternatively, range from0.9:1 to 1.02:1. In yet other embodiments, the molar ratio of primaryamine to α-diacyl compound can be about 1:1. In yet other embodiments,the molar ratio of primary amine to α-diacyl compound can be greaterthan 1:1 when the remaining acyl group of the resultant α-acyliminecompound does not readily react with additional equivalents of theprimary amine under the reaction conditions employed. In thisembodiment, the use of excess primary amine can prove desirable.

Generally, whenever an α-diacyl compound is contacted with a metal salt,e.g. to form an α-acylimine metal complex by contacting an α-diacylcompound, a primary amine, and metal salt, the molar ratio of metal saltto α-diacyl compound can be any molar ratio capable of producing anα-acylimine metal complex. In some embodiments, the molar ratio of metalsalt to α-diacyl compound to is greater than 0.75:1; alternatively,greater than 0.85:1; alternatively, greater than 0.9:1; oralternatively, greater than 0.95:1. In other embodiments, the molarratio of metal salt to α-diacyl compound can range from 0.75:1 to1.25:1; alternatively, range from 0.85:1 to 1.15:1; or alternatively,range from 0.9:1 to 1.1:1. In yet other embodiments, the molar ratio ofmetal salt to α-diacyl compound can be about 1:1.

Generally, whenever primary amine is contacted with a metal salt, e.g.to form an α-acylimine metal complex or an α-diimine metal complex, themolar ratio of primary amine to metal salt can be any molar ratiocapable of producing the acylimine metal complex or the α-diimine metalcomplex. In some embodiments, the molar ratio of primary amine to metalsalt can be less than 1.1:1; alternatively, less than 1.05:1;alternatively, less than 1.02:1; or alternatively, less than 1:1. In yetother embodiments, molar ratio of amine to metal salt can range from0.75:1 to 1.1:1; alternatively, range from 0.85:1 to 1.05:1; oralternatively, range from 0.9:1 to 1.02:1. In certain embodiments, themolar ratio of amine to metal salt can be about 1:1.

Generally, whenever an α-diacyl compound is contacted with a primaryamine and a metal salt, e.g. to form an α-acylimine metal complex, themolar ratio of the primary amine to metal salt can be any molar ratiocapable of producing an α-acylimine metal complex. In some embodiments,the molar ratio of primary amine to metal salt to α-diacyl compound canrange from 0.75:1:1 to 1.1:1:1; alternatively, range from 0.85:1:1 to1.05:1:1; or alternatively, range from 0.9:1:1 to 1.02:1:1. In certainembodiments, the molar ratio of primary amine to metal salt to α-diacylcompound is about 1:1:1.

Generally, whenever an α-acylimine compound is contacted with a metalsalt, e.g. to form an α-acylimine metal complex or an α-diimine metalcomplex, the molar ratio of metal salt to α-acylimine compound can beany ratio capable of producing the α-acylimine metal complex or theα-diimine metal complex. In some embodiments, the molar ratio of metalsalt to α-acylimine compound is greater than 0.75:1; alternatively,greater than 0.85:1; alternatively, greater than 0.9:1; oralternatively, greater than 0.95:1. In other embodiments, the molarratio of metal salt to α-acylimine compound ranges from 0.75:1 to1.25:1; alternatively, ranges from 0.85:1 to 1.15:1; or alternatively,ranges from 0.9:1 to 1.1:1. In yet other embodiments, the molar ratio ofmetal salt to α-acylimine compound is about 1:1.

Generally, whenever a primary amine is contacted with an α-acyliminecompound, e.g. to form an α-diimine compound or an α-diimine metalcomplex, the molar ratio of primary amine to α-acylimine compound is anyprimary amine to α-acylimine compound molar ratio capable of producingthe α-diimine compound or the α-diimine metal complex. In someembodiments, the molar ratio of primary amine to α-acylimine compoundcan be less than 1.25:1; alternatively, less than 1.15 to 1; oralternatively, less than 1.1:1. The molar ratio of primary amine toα-acylimine compound can range from 0.75:1 to 1.25:1; alternatively,range from 0.85:1 to 1.15:1; or alternatively, range from 0.9:1 to1.1:1. In certain embodiments, the molar ratio of primary amine toα-acylimine compound is about 1:1. In yet other embodiments, the molarratio of primary amine to α-diimine compound can be greater than 1:1when the initial imine group is not readily displaced with the primaryamine under the reaction conditions employed. In this embodiment, theuse of excess primary amine can prove desirable.

Generally, whenever a primary amine, α-acylimine compound, and a metalsalt are contacted, e.g. to form an α-diimine metal complex, the molarratio of primary amine to α-acylimine compound to metal salt toα-acylimine compound is any primary amine to metal salt to α-diacylcompound molar ratio capable of producing the α-diimine metal complex.In some embodiments, the molar ratio of primary amine to metal salt toα-acylimine compound can range from 0.75:1:1 to 1.1:1:1; alternatively,range from 0.85:1:1 to 1.05:1:1; or alternatively, range from 0.9:1:1 to1.02:1:1. In certain embodiments, the molar ratio of amine toα-acylimine compound to metal salt can be about 1:1:1.

Generally, whenever a primary amine is contacted with an α-acyliminemetal complex, e.g. to form an α-diimine metal complex, the molar ratioof primary amine to α-acylimine metal complex can be any primary amineto α-acylimine metal complex molar ratio capable of producing theα-diimine metal complex. In some embodiments, the molar ratio of primaryamine to α-acylimine metal complex can be greater than 0.9:1;alternatively, greater than 0.95:1; or alternatively, greater than0.975:1. In other embodiments, the molar ratio of primary amine toα-acylimine metal complex ranges from 0.9:1 to 1.5:1; alternatively,from 0.95:1 to 1:25:1; or alternatively, from 0.975:1 to 1.1:1. Incertain embodiments, the molar ratio of amine to α-acylimine metalcomplex is about 1:1.

Generally, the solvent for preparing the α-acylimine compound,α-acylimine metal complex, or α-diimine metal complex can be any solventcapable of allowing the selected reagents to react to form the selectedcompound or metal complex. In embodiments, the solvent can be analcohol, ether, nitrite or halogenated hydrocarbon. In some embodiments,the solvent can be an alcohol; alternatively, and ether; alternatively,a nitrite; or alternatively, a halogenated hydrocarbon. Generally, thealcohol, ether, nitrite, or halogenated hydrocarbon can be any C₁ to C₁₀alcohol, C₁ to C₁₀ ether, C₁ to C₁₀ nitrite or C₁ to C₁₀ halogenatedhydrocarbon; or alternatively, any C₁ to C₅ alcohol, ether, C₁ to C₅nitrite, or C₁ to C₅ halogenated hydrocarbon. In some embodiments, thealcohol solvent can be methanol, ethanol, propanol, isopropanol,butanol, or tert-butanol. In other embodiments, the ether can bedimethyl ether, diethyl ether, methyl ethyl ether, monoethers ordiethers of glycols (e.g. dimethyl glycol ether), furans, dihydrofuran,substituted dihydrofurans, tetrahydrofuran (THF), tetrahydropyrans,1,3-dioxanes, or 1,4-dioxanes. In other embodiments, the nitrite solventcan be acetonitrile. In yet other embodiments, the halogenatedhydrocarbon can be methylene chloride, chloroform, carbon tetrachloride,or 1,2-dichloroethane. In some particular embodiments, the solvent canbe methanol; alternatively, ethanol; alternatively, isopropanol;alternatively, tetrahydrofuran; alternatively, acetonitrile;alternatively, methylene chloride; or alternatively, chloroform.

Generally, the formation of at least one imine bond of α-diimine metalcomplex in the presence of a metal salt or metal complex (e.g. reactionbetween a primary amine and α-acylimine metal complex or a reactionbetween a primary amine, metal salt and an α-acylimine compound) can becarried out at any suitable reaction conditions capable of producing theα-diimine metal complex. For example, the time, temperature, and/orpressure required to produce the α-diimine metal complex by forming atleast one imine bond of α-diimine metal complex in the presence of ametal salt or metal complex can be any condition needed to produce aquantity of the α-diimine metal complex. Provided the teachings of thepresent disclosure, a skilled artisan may recognize the relationshipbetween parameters, such as the temperature of the imine bond formationreaction and the time necessary to form a quantity of the α-diiminemetal complex, and how to suitably vary such parameters. Additionally,provided the teachings of the present disclosure, the skilled artisanmay also recognize that an imine bond formation reaction can also bedependent upon other reaction parameters such as molar ratio ofreagents, and can vary the reaction parameters such as reagent moleratio, reaction time, and/or reaction temperature to obtain desiredresults.

Generally, the formation of at least one imine bond of α-diimine metalcomplex in the presence of a metal salt or metal complex (e.g. reactionbetween a primary amine and α-acylimine metal complex or a reactionbetween a primary amine, metal salt and an α-acylimine compound) can becarried out at any suitable reaction conditions capable of producing theα-diimine metal complex. For example, the time, temperature, and/orpressure required to produce the α-diimine metal complex by forming atleast one imine bond of α-diimine metal complex in the presence of ametal salt or metal complex can be any condition needed to produce aquantity of the α-diimine metal complex. Provided the teachings of thepresent disclosure, a skilled artisan may recognize the relationshipsbetween parameters, such as the temperature of the imine bond formationreaction and the time necessary to form a quantity of the α-diiminemetal complex, and how to suitably vary such parameters. Additionally,provided the teachings of the present disclosure, the skilled artisanmay also recognize that an imine bond formation reaction can also bedependent upon other reaction parameters such as molar ratio ofreagents, and can vary the reaction parameters such as reagent moleratio, reaction time, and/or reaction temperature to obtain desiredresults.

In some embodiments, the reaction to form at least one imine bond of theα-diimine metal complex in the presence of a metal salt or metal complexcan occur at a temperature ranging from −20° C. to 200° C. In otherembodiments, the reaction to form at least one imine bond of theα-diimine metal complex in the presence of a metal salt or metal complexcan occur at a temperature ranging from 0° C. to 150° C.; alternatively,from 20° C. to 100° C.; or alternatively, from 40° C. to 80° C. The timeneeded to form at least one imine bond of resulting α-diimine metalcomplex in the presence of a metal salt or metal complex, at thetemperature described herein, may be from less than 1 minute to 48hours; alternatively, from 30 minutes to 36 hours; or alternatively,from 1 hours to 24 hours. The temperatures and times described hereinare generally applicable to any methods of forming at least one iminebond in the presence of a metal salt or metal complex including themethods for contacting an α-diacyl compound, a metal salt and a primaryamine, contacting an α-acylimine compound, a metal salt, and a primaryamine, or contacting an α-acylimine metal complex and a primary amine.

In embodiments, the step wherein the imine bond of the α-diimine metalcomplex is formed in the presence of a metal salt or metal complexproceeds at a yield of greater than 60 percent based on the weight ofthe limiting reagent. In some embodiments, the step wherein the iminebond of the α-diimine metal complex is formed in the presence of a metalsalt or metal complex proceeds at a yield of greater than about 65percent based on the weight of the limiting reagent; alternatively,greater than 70 percent based on the weight of the limiting reagent;alternatively, greater than 75 percent based on the weight of thelimiting reagent; alternatively, greater than 80 percent based on theweight of the limiting reagent; alternatively, greater than 85 percentbased on the weight of the limiting reagent; or alternatively, greaterthan 90 percent based on the weight of the limiting reagent.

Generally, the procedures described herein enable the production ofspecific α-diimine metal complexes having two different (or twodifferent type) imine groups in a high yield using an α-diacyl compoundand two different (or two different type) primary amines. Not to bebound by theory, it is believed that the reaction of the second aminewith an α-acylimine compound in the presence of a metal salt, orreaction of the second amine with an α-acylimine metal complex, inhibitsthe reversibility of the Schiff base reaction that formed the firstimine group of the α-acylimine compound. Normally, the reversibility ofthe Schiff base reaction does not create issues when the two primaryamines used to produce the two imine group of the α-diimine compound(and ultimately the α-diimine metal complex) are the same. However, whenthe two different primary amines are used to produce two different iminenitrogen groups, the reversibility of the Schiff base reaction allowsthe α-acylimine compound to revert into its component primary amine andα-diacyl compound and thus allows the formation of all potentialα-diimine compounds. Thus, the presence of the metal salt or α-acyliminemetal complex during the formation of α-diimine metal complex allowsimproved selectivity to a specific desired α-diimine metal complex basedupon the limiting reagent of the synthesis method.

In embodiments, α-diimine metal complex is produced at an overall yieldof greater than 50 percent based on the weight of the limiting reagent;alternatively, greater than 55 percent based on the weight of thelimiting reagent; alternatively, the greater than about 60 percent basedon the weight of the limiting reagent; alternatively, greater than 65percent based on the weight of the limiting reagent; alternatively,greater than 70 percent based on the weight of the limiting reagent;alternatively, greater than 75 percent based on the weight of thelimiting reagent; or alternatively, greater than 80 percent based on theweight of the limiting reagent. In some embodiments, the limitingreagent for determination of the overall yield can be the α-diacylcompound. In other embodiments, the limiting reagent for determinationof the overall yield is the can be the first primary amine.

Olefin Polymerization or Oligomerization

The α-diimine metal complexes described in the present application canbe employed in the polymerization and/or oligomerization of olefins.Such a process can be carried out by contacting a catalyst systemcomprising an α-diimine metal complex with one or more olefin monomersunder reaction conditions suitable for polymerization or oligomerizationof olefins. In some embodiments, the polymerization or oligomerizationprocess comprises 1) contacting an olefin, an α-diimine metal complex,and a cocatalyst; and 2) forming an olefin polymer or oligomer. In otherembodiments, the polymerization or oligomerization process is an alphaolefin production process comprising: 1) contacting ethylene, anα-diimine metal complex, and a cocatalyst; and 2) forming a productstream comprising alpha olefins. In other embodiments, thepolymerization or oligomerization process is an alpha olefin productionprocess comprising: 1) contacting ethylene, an α-diimine metal complex,and a cocatalyst; and 2) forming a product stream comprisingpolyethylene. The process can comprise additional steps such asdeactivating the catalyst and isolating the olefin oligomer or polymer.Suitable monomers for the olefin polymerization or oligomerization canbe olefins having 2 to 20 carbon atoms; alternatively, olefins having 2to 3 carbon atoms; alternatively, ethylene; or alternatively, propylene.

Olefin Polymerization or Oligomerization Catalysts and Cocatalysts

Within the polymerization or oligomerization processes, the α-diiminemetal complex can be any α-diimine metal complex described hereincapable of forming the desired polymer or oligomer. In embodiments, theα-diimine metal complex can be a metal salt complexed to an α-diiminecompound comprising 1) an α-diimine group derived from an α-diacylcompound and 2) two different α-diimine nitrogen groups. In othernon-limiting embodiments, the α-diimine metal complex can be a metalsalt complexed to an α-diimine compound comprising 1) an α-diimine groupderived from an α-diacyl compound and 2) two different α-diiminenitrogen groups consisting of an organyl groups consisting of inertfunctional groups, hydrocarbyl groups, or mixture thereof;alternatively, a metal salt complexed to an α-diimine compoundconsisting of 1) an α-diimine group derived from an α-diacyl compoundand 2) a first imine nitrogen group consisting of an organyl groupconsisting of inert functional groups or a hydrocarbyl group and 3) asecond imine nitrogen group comprising a metal salt complexing group; oralternatively, a metal salt complexed to an α-diimine compoundconsisting of 1) an α-diimine group derived from an α-diacyl compoundand 2) a first imine nitrogen group consisting an organyl groupconsisting of inert functional groups or a hydrocarbyl group and 3) asecond imine group comprising a metal salt complexing group and alinking group linking the metal salt complexing group to the secondimine nitrogen atom. As the metal salt, α-diacyl compound from which theα-diimine compound is derived, and the two imine groups originate fromindependent elements, the α-diimine metal complex utilized to polymerizeor oligomerize olefins can be further described using any combination ofthe metal salt as described herein, the α-diacyl compound from which theα-diimine compound is derived as described herein, any first iminenitrogen group as described herein, any second imine nitrogen groupmetal salt complexing group as described herein, and any linking grouplinking the metal salt complexing group to the of the second iminenitrogen group as described herein. Alternatively, the α-diimine metalcomplexes utilized for the polymerization or oligomerization of olefinscan be described using the alternative α-diimine metal complexdescriptions equivalent to the polymerization or oligomerizationα-diimine metal complexes indicated herein.

The process to produce alpha olefins can utilize any α-diimine metalcomplex capable of producing alpha olefins. In non-limiting embodiments,the α-diimine metal complex capable of producing alpha olefins can be ametal salt complexed to an α-diimine compound comprising 1) an α-diiminegroup derived from an α-diacyl compound and 2) a first imine nitrogengroup consisting of an organyl group consisting of inert functionalgroups or a hydrocarbyl group and 3) a second imine nitrogen groupcomprising a metal salt complexing group and a linking group linking themetal salt complexing group to the second imine nitrogen atom; oralternatively, a metal salt complexed to an α-diimine compoundconsisting of 1) an α-diimine group derived from an α-diacyl compoundand 2) a first imine nitrogen group consisting of an organyl groupconsisting of inert functional groups or a hydrocarbyl group and 3) asecond imine nitrogen group consisting of a metal salt complexing groupand a linking group linking the metal salt complexing group to thesecond imine nitrogen atom. As the metal salt, α-diacyl compound fromwhich the α-diimine compound is derived, and the two imine groupsoriginate from independent elements, the α-diimine metal complex capableof producing alpha olefins can be further described using anycombination of the metal salt as described herein, the α-diacyl compoundfrom which the α-diimine compound is derived as described herein, anyfirst imine nitrogen group as described herein, any second iminenitrogen group metal salt complexing group as described herein, and anylinking group linking the metal salt complexing group to the of thesecond imine nitrogen group as described herein. Alternatively, theα-diimine metal complexes utilized for the production of alpha olefinscan be described using the alternative α-diimine metal complexdescriptions equivalent to alpha olefin production α-diimine metalcomplexes indicated herein.

The metal salt of the α-diimine metal complex capable of producing alphaolefins can be any metal salt as described herein. In embodiments, themetal salt can comprise iron, cobalt, or mixtures thereof. In someembodiments, the metal salt can comprise iron or cobalt. In someembodiments, the metal salt can comprise iron; or alternatively,comprise cobalt.

The α-diacyl compound from which the α-diimine group of the α-diiminemetal complex capable of producing alpha olefins is derived can be anyα-diacyl compound as described herein. In embodiments, the α-diiminegroup can be derived from an aromatic α-diacyl compound. In someembodiments, the α-diimine group of the α-diimine metal complex can bederived from acenaphthenequinone, a substituted acenaphthenequinone,phenanthrenequinone, a substituted phenanthrenequinone, pyrenequinone,or a substituted pyrenequinone. In other embodiments, the α-diiminegroup of the α-diimine metal complex can be derived fromacenaphthenequinone, phenanthrenequinone, or pyrenequinone. In yet otherembodiments, the α-diimine group of the α-diimine metal complex can bederived from acenaphthenequinone; alternatively, phenanthrenequinone; oralternatively, pyrenequinone.

The first imine nitrogen group within the α-diimine group of someα-diimine metal complexes capable of producing alpha olefins can be anyorganyl group consisting of inert functional groups or a hydrocarbylgroup as described herein. In an aspect, the organyl group consisting ofinert functional groups of the first imine nitrogen group can consist ofa phenyl group or a substituted phenyl group (substituted phenyl groupconsisting of inert functional groups). In embodiments, the hydrocarbylgroup of the first imine nitrogen group can consist of a phenyl group ora substituted phenyl group. In some embodiments, the hydrocarbyl groupof the first imine nitrogen group can be a 2-substituted phenyl group;alternatively, a 2,6-disubsituted phenyl group; or alternatively, a2,4,6-trisubstituted phenyl group. In other embodiments, the hydrocarbylgroup of the first imine nitrogen group can be a 2,6-dimethylphenylgroup, a 2,6-diethylphenyl group, a 2,6-diisopropylphenyl group, or a2,6-di-tert-butylphenyl group. In yet other embodiments, the hydrocarbylgroup of the first imine nitrogen group can be a 2,6-dimethylphenylgroup, a 2,6-diethylphenyl group, or a 2,6-diisopropylphenyl group. Infurther embodiments, the hydrocarbyl group of the first imine nitrogengroup can be a 2,6-dimethylphenyl group; alternatively, a2,6-diethylphenyl group; alternatively, a 2,6-diisopropylphenyl group;alternatively, a 2,6-di-tert-butylphenyl group; or alternatively, a2,4,6-trimethylphenyl group (mesityl group).

Particular combinations of the metal salt complexing group and linkinggroup linking the metal salt complexing group to the second iminenitrogen atom within the α-diimine compound of the α-diimine metalcomplex can be advantageous for producing alpha olefins. In aspects, thesecond imine group can comprise a dialkyl aminyl group, a diphenylaminyl group, a substituted diphenyl aminyl group a dialkyl phosphinylgroup, a diphenyl phosphinyl group, or a substituted diphenyl phosphinylgroup and —(CH₂)_(m)— linking group where m is 2 or 3; alternatively,can comprise a pyridinyl group, a substituted pyridinyl group, a furanylgroup, a substituted furanyl group, a thiophenyl group, or a substitutedthiophenyl group and a —(CH₂)— linking group; or alternatively, cancomprise an alkyl etheryl group, a phenyl etheryl group, a substitutedphenyl etheryl group, an alkyl sulfidyl group, a phenyl sulfidyl group,or a substituted phenyl sulfidyl group and a —(CH₂CH₂)— linking group.Alternatively, the second imine nitrogen group can comprise a dialkylaminyl group, a diphenyl aminyl group, a dialkyl phosphinyl group, or adiphenyl phosphinyl group and a —(CH₂)_(m)— linking group where m is 2or 3; alternatively, can comprise a pyridinyl group, a furanyl group, ora thiophenyl group and a —(CH₂)— linking group; alternatively, cancomprise an alkyl etheryl group or an alkyl sulfidyl group and a—(CH₂CH₂)— linking group; or alternatively, can comprise a phenyletheryl group or an phenyl sulfidyl group and a —(CH₂CH₂)— linkinggroup. In some embodiments, the second imine group can comprise adiphenyl aminyl group, a substituted diphenyl aminyl group, a diphenylphosphinyl group, or substituted a diphenyl phosphinyl group and a—(CH₂)_(m)— linking group where m is 2 or 3; alternatively, can comprisea diphenyl aminyl group or a diphenyl phosphinyl group and a —(CH₂)_(m)—linking group where m is 2 or 3; alternatively, can comprise asubstituted diphenyl aminyl group, or a substituted diphenyl phosphinylgroup and a —(CH₂)_(m)— linking group where m is 2 or 3; alternatively,can comprise a diphenyl phosphinyl group or a substituted diphenylphosphinyl group and a —(CH₂)_(m)— linking group where m is 2 or 3;alternatively, can comprise a diphenyl phosphinyl group and a—(CH₂)_(m)— linking group where m is 2 or 3; alternatively, can comprisea substituted diphenyl phosphinyl group and a —(CH₂)_(m)— linking groupwhere m is 2 or 3; alternatively, can comprise a diphenyl phosphinylgroup or a substituted diphenyl phosphinyl group and a —(CH₂CH₂)—linking group; alternatively, can comprise a diphenyl phosphinyl groupand a —(CH₂CH₂)— linking group; alternatively, can comprise asubstituted diphenyl phosphinyl group and a —(CH₂CH₂)— linking group;alternatively, can comprise a 2-pyridinyl group or a substituted2-pyridinyl group and a —(CH₂)— linking group; alternatively, a2-pyridinyl group and a —(CH₂)— linking group; alternatively, asubstituted 2-pyridinyl group and a —(CH₂)— linking group;alternatively, can comprise a phenyl etheryl group, a substituted phenyletheryl group, a phenyl sulfidyl group, or a substituted phenyl sulfidylgroup and a —(CH₂CH₂)— linking group; alternatively, can comprise aphenyl etheryl group, or a phenyl sulfidyl group and a —(CH₂CH₂)—linking group; alternatively, can comprise a substituted phenyl etherylgroup, or a substituted phenyl sulfidyl group and a —(CH₂CH₂)— linkinggroup; alternatively, can comprise a phenyl sulfidyl group or asubstituted phenyl sulfidyl group and a —(CH₂CH₂)— linking group;alternatively, can comprise a phenyl sulfidyl group and a —(CH₂CH₂)—linking group; or alternatively, can comprise a substituted phenylsulfidyl group and a —(CH₂CH₂)— linking group.

In other aspects, the second imine group can consist of a dialkyl aminylgroup, a diphenyl aminyl group, a substituted diphenyl aminyl group adialkyl phosphinyl group, a diphenyl phosphinyl group, or a substituteddiphenyl phosphinyl group and —(CH₂)_(m)— linking group where m is 2 or3; alternatively, can consist of a pyridinyl group, a substitutedpyridinyl group, a furanyl group, a substituted furanyl group, athiophenyl group, or a substituted thiophenyl group and a —(CH₂)—linking group; or alternatively, can consist of an alkyl etheryl group,a phenyl etheryl group, a substituted phenyl etheryl group, an alkylsulfidyl group, a phenyl sulfidyl group, or a substituted phenylsulfidyl group and a —(CH₂CH₂)— linking group. Alternatively, the secondimine nitrogen group can consist of a dialkyl aminyl group, a diphenylaminyl group, a dialkyl phosphinyl group, or a diphenyl phosphinyl groupand a —(CH₂)_(m)— linking group where m is 2 or 3; alternatively, canconsist of a pyridinyl group, a furanyl group, or a thiophenyl group anda —(CH₂)— linking group; alternatively, can consist of an alkyl etherylgroup or an alkyl sulfidyl group and a —(CH₂CH₂)— linking group; oralternatively, can consist of a phenyl etheryl group or an phenylsulfidyl group and a —(CH₂CH₂)— linking group. In some embodiments, thesecond imine group can consist of a diphenyl aminyl group, a substituteddiphenyl aminyl group, a diphenyl phosphinyl group, or substituted adiphenyl phosphinyl group and a —(CH₂)_(m)— linking group where m is 2or 3; alternatively, can consist of a diphenyl aminyl group or adiphenyl phosphinyl group and a —(CH₂)_(m)— linking group where m is 2or 3; alternatively, can consist of a substituted diphenyl aminyl group,or a substituted diphenyl phosphinyl group and a —(CH₂)_(m)— linkinggroup where m is 2 or 3; alternatively, can consist of a diphenylphosphinyl group or a substituted diphenyl phosphinyl group and a—(CH₂)_(m)— linking group where m is 2 or 3; alternatively, can consistof a diphenyl phosphinyl group and a —(CH₂)_(m)— linking group where mis 2 or 3; alternatively, can consist of a substituted diphenylphosphinyl group and a —(CH₂)_(m)— linking group where m is 2 or 3;alternatively, can consist of a diphenyl phosphinyl group or asubstituted diphenyl phosphinyl group and a —(CH₂CH₂)— linking group;alternatively, can consist of a diphenyl phosphinyl group and a—(CH₂CH₂)— linking group; alternatively, can consist of a substituteddiphenyl phosphinyl group and a —(CH₂CH₂)— linking group; alternatively,can consist of a 2-pyridinyl group or a substituted 2-pyridinyl groupand a —(CH₂)— linking group; alternatively, a 2-pyridinyl group and a—(CH₂)— linking group; alternatively, a substituted 2-pyridinyl groupand a —(CH₂)— linking group; alternatively, can consist of a phenyletheryl group, a substituted phenyl etheryl group, a phenyl sulfidylgroup, or a substituted phenyl sulfidyl group and a —(CH₂CH₂)— linkinggroup; alternatively, can consist of a phenyl etheryl group, or a phenylsulfidyl group and a —(CH₂CH₂)— linking group; alternatively, canconsist of a substituted phenyl etheryl group, or a substituted phenylsulfidyl group and a —(CH₂CH₂)— linking group; alternatively, canconsist of a phenyl sulfidyl group or a substituted phenyl sulfidylgroup and a —(CH₂CH₂)— linking group; alternatively, can consist of aphenyl sulfidyl group and a —(CH₂CH₂)— linking group; or alternatively,can consist of a substituted phenyl sulfidyl group and a —(CH₂CH₂)—linking group.

In a non-limiting aspect, the α-diimine metal complex capable ofproducing alpha olefins can comprise a metal salt comprising ironcomplexed to an α-diimine compound comprising 1) an α-diimine groupderived from aromatic dione; 2) a first imine nitrogen group consistingof a 2,6-disubstituted phenyl group; and 3) a second imine nitrogengroup comprising a metal salt complexing group and a linking grouplinking the metal salt complexing group to the second imine nitrogenatom; or alternatively, a metal salt comprising iron complexed to anα-diimine compound comprising 1) an α-diimine group derived fromaromatic dione; 2) a first imine nitrogen group consisting of a2,6-disubstituted phenyl group; and 3) a second imine nitrogen groupconsisting of a metal salt complexing group and a linking group linkingthe metal salt complexing group to the second imine nitrogen atom. Insome non-limiting embodiments, the α-diimine metal complex capable ofproducing alpha olefins can comprise a metal salt comprising ironcomplexed to an α-diimine compound comprising 1) an α-diimine groupderived from acenaphthenequinone, phenanthrenequinone, or pyrenequinone;2) a first imine nitrogen group consisting of a 2,6-dimethylphenylgroup, a 2,6-diethylphenyl group, or a 2,6-diisopropylphenyl group; and3) a second imine nitrogen group comprising a metal salt complexinggroup and a linking group linking the metal salt complexing group to thesecond imine nitrogen atom. In other non-limiting embodiments, theα-diimine metal complex capable of producing alpha olefins can comprisea metal salt comprising iron complexed to an α-diimine compoundcomprising 1) an α-diimine group derived from acenaphthenequinone,phenanthrenequinone, or pyrenequinone; 2) a first imine nitrogen groupconsisting of a 2,6-dimethylphenyl group, a 2,6-diethylphenyl group, ora 2,6-diisopropylphenyl group; and 3) a second imine nitrogen groupconsisting of a metal salt complexing group and a linking group linkingthe metal salt complexing group to the second imine nitrogen atom.Further embodiments of the elements of the α-diimine metal complexcapable of producing alpha olefins are described herein.

Generally, the cocatalyst can be any organometallic compound capable ofactivating the α-diimine metal complex to polymerize or oligomerizeolefins. Suitable cocatalysts can include monomeric or oligomeric metalalkyls, metal aryls, metal alkyl-aryls comprising at least one of themetals selected from the group consisting of B, Al, Be, Mg, Ca, Sr, Ba,Li, Na, K, Rb, Cs, Zn, Cd, and Sn. In embodiments, the cocatalyst can beselected from the group consisting of organoaluminum compounds,organoboron compounds, organolithium compounds, or mixtures thereof. Insome embodiments, the cocatalyst can be an organoaluminum compound.Applicable organoaluminum compounds can include trialkylaluminums,alkylaluminum halides, alumoxanes or mixture thereof. In someembodiments, the organoaluminum compound can be trimethylaluminumtriethylaluminum, diethylaluminum chloride, diethylaluminum ethoxide,diethylaluminum cyanide, diisobutylaluminum chloride,triisobutylaluminum, ethylaluminum sesquichloride, methylalumoxane(MAO), modified methylalumoxane (MAO), isobutyl alumoxanes, t-butylalumoxanes, or mixtures thereof. In other embodiments, theorganoaluminum compounds can include methylalumoxane (MAO), modifiedmethylalumoxane (MMAO), isobutyl alumoxanes, t-butyl alumoxanes, ormixtures thereof. In other embodiments, the cocatalyst can bemethylalumoxane, modified methylalumoxane, or mixtures thereof. In yetother embodiments, the cocatalyst can be methylalumoxane; alternatively,modified methylalumoxane; isobutylalumoxane (IBAO); or alternatively,partially hydrolyzed trialkylaluminum.

In embodiments, the molar ratio of the metal of the cocatalyst to themetal of the α-diimine metal complex can range from 1:1 to 10,000:1;alternatively, from 10:1 to 5,000:1; or alternatively, from 100:1 to3,000:1; or alternatively, from 200:1 to 2,000:1. In embodiments whereinthe α-diimine metal complex comprises a iron salt and the cocatalyst isan alumoxane the molar ratio of aluminum to iron can range from 1:1 to10,000:1; alternatively, from 10:1 to 5,000:1; alternatively, from 100:1to 3,000:1; or alternatively, from 200:1 to 2,000:1.

The α-diimine metal complex, cocatalyst(s), and olefin can be contactedin any manner known to those skilled in the art. For instance, theα-diimine metal complex and the cocatalyst can be mixed first beforebringing into contact with a feed comprising an olefin or an olefinmixture. Alternatively, the cocatalyst can be mixed with the olefinand/or the solvent prior to contact with the α-diimine metal complex.

Polymerization or Oligomerization Solvents, Reactors, ReactionConditions and Products

In embodiments, the polymerization or oligomerization reaction can occurin a solvent or diluent. In some embodiments, the solvent or diluent cancomprise a C₄ to C₂₀ hydrocarbon; or alternatively, a C₄ to C₁₀hydrocarbon. The hydrocarbon solvent can be a saturated hydrocarbon, anaromatic hydrocarbon or an olefinic hydrocarbon. In some embodiments,the saturated hydrocarbon solvent can be a C₄ to C₁₀ saturatedhydrocarbon. In other embodiments, the saturated solvent can be butane,isobutane, hexane, heptane, cyclohexane, or mixtures thereof. In someembodiments, the aromatic solvent can be a C₆ to C₂₀ aromatic compound.In some embodiments, the aromatic solvent can be benzene, toluene,xylene(s), ethylbenzene, or mixtures thereof. In other embodiments,another embodiment, the olefinic hydrocarbon solvent can comprise alphaolefins. In other embodiments, the alpha olefin solvent comprises a C₄to C₂₀ alpha olefin; alternatively, a C₄ to C₁₂ alpha olefin;alternatively, alternatively, a C₁₂ to C₁₈ alpha olefin. In yet otherembodiments, the alpha olefin solvent can be 1-butene, 1-dodecene,1-tetradecene, 1-hexadecene, 1-octadecene, or combinations thereof.

Unless specified otherwise, the terms contacted, combined, and “in thepresence of” refer to any addition sequence, order, or concentration forcontacting or combining two or more components of the polymerizationreaction. Combining or contacting of polymerization or oligomerizationcomponents, according to the various methods described herein may occurin one or more contact zones under suitable contact conditions such astemperature, pressure, contact time, flow rates, etc. . . . The contactzone can be disposed in a vessel, e.g. a storage tank, tote, container,mixing vessel, reactor, etc.; a length of pipe, e.g. a tee, inlet,injection port, or header for combining component feed lines into acommon line; or any other suitable apparatus for bringing the componentsinto contact. The methods may be carried out in a batch or continuousprocess as is suitable for a given embodiment, with physical parametersof the contact zone being specified accordingly.

In embodiments, the polymerization or oligomerization can be acontinuous process carried out in one or more reactors. In someembodiments, the continuous polymerization or oligomerization processreactor can comprise a loop reactor, a tubular reactor, a continuousstirred tank reactor (CSTR), or combinations thereof. In otherembodiments, the continuous polymerization or oligomerization processreactor can be a loop reactor; alternatively, a tubular reactor; oralternatively, a continuous stirred tank reactor (CSTR). In otherembodiments, the continuous polymerization or oligomerization processreactor can be employed in the form of different types of continuousreactors in combination, and in various arrangements. In an embodiment,the continuous reactor can be a combination of a tubular reactor and aCSTR. In other embodiments, the continuous polymerization oroligomerization process reactor can be two or more reactors in series,two or more reactors in parallel, or combinations thereof. In anembodiment, the continuous polymerization or oligomerization processreactor can be more than one CSTR in series. In another embodiment, thecontinuous reactor can be a tubular reactor and a loop reactor inseries. In yet another embodiment, the continuous reactor can be two ormore loop reactors in series.

Suitable polymerization or oligomerization reaction conditions such astemperatures, pressures and times can be impacted by a number of factorssuch as α-diimine metal complex identity, α-diimine metal complexstability, α-diimine metal complex activity, cocatalyst identity,cocatalyst activity, desired product (e.g. polyethylene versus alphaolefins), desired product distribution, and/or desired product purityamong others. Provided the teachings of the present disclosure, oneskilled in the art will recognize how to adjust the polymerization oroligomerization reaction conditions to achieve the desired objectives.

The reaction temperature of the polymerization or oligomerizationreaction can be any reaction temperature required to produce the desiredpolymerization or oligomerization product (such as polyethylene or alphaolefins). In some embodiments, the reaction temperature for thepolymerization or oligomerization reaction can range from −20° C. to200° C. In some embodiments, the polymerization or oligomerizationtemperature ranges from 0° C. to 150° C.; alternatively, ranges from 10°C. to 150° C.; alternatively, ranges from 20° C. to 100° C.; oralternatively, ranges from 30° C. to 80° C.

The reaction pressure of the polymerization or oligomerization reactioncan be any reaction pressure required to produce the desiredpolymerization or oligomerization product (such as polyethylene or alphaolefins). In some embodiments, the polymerization or oligomerizationreaction pressure can be greater than 0 psig (0 KPa); alternatively,greater than 50 psig (344 KPa); alternatively, greater than 100 psig(689 KPa); or alternatively, greater than 150 psig (1.0 MPa). In otherembodiments, the polymerization or oligomerization reaction pressure canrange from 0 psig (0 KPa) to 5,000 psig (34.5 MPa); alternatively, 50psig (344 KPa) to 4,000 psig (27.6 MPa); alternatively, 100 psig (689KPa) to 3,000 psig (20.9 MPa); or alternatively, 150 psig (1.0 MPa) to2,000 psig (13.8 MPa). In embodiments wherein the monomer is a gas (e.g.ethylene), the polymerization or oligomerization reaction can be carriedout under a monomer gas pressure. When the polymerization oroligomerization reaction produces polyethylene or alpha olefins, thereaction pressure can be the monomer ethylene pressure. In someembodiments, the ethylene pressure can be greater than 0 psig (0 KPa);alternatively, greater than 50 psig (344 KPa); alternatively, greaterthan 100 psig (689 KPa); or alternatively, greater than 150 psig (1.0MPa). In other embodiments, the ethylene pressure can range from 0 psig(0 KPa) to 5,000 psig (34.5 MPa); alternatively, 50 psig (344 KPa) to4,000 psig (27.6 MPa); alternatively, 100 psig (689 KPa) to 3,000 psig(20.9 MPa); or alternatively, 150 psig (1.0 MPa) to 2,000 psig (13.8MPa). In some cases when ethylene is the monomer, inert gases can form aportion of the total reaction pressure. In the cases where inert gasesform a portion of the reaction pressure, the previously stated ethylenepressures can be the applicable ethylene partial pressures of thepolymerization or oligomerization reaction. In the situation where themonomer provides all or a portion of the polymerization oroligomerization reaction pressure, the reaction system pressure candecrease as the gaseous monomer is consumed. In this situation,additional gaseous monomer and/or inert gas can be added to maintain adesired polymerization or oligomerization reaction pressure. Inembodiments, additional gaseous monomer can be added to thepolymerization or oligomerization reaction at a set rate (e.g. for acontinuous flow reactor), at different rates (e.g. to maintain a setsystem pressure in a batch reactor). In other embodiments, thepolymerization or oligomerization reaction pressure can be allowed todecrease without adding any additional gaseous monomer and/or inert gas.

The reaction time of the polymerization or oligomerization reaction canbe any reaction time required to produce the desired quantity ofpolymerization or oligomerization product (such as polyethylene or alphaolefins), obtain a desired catalyst productivity, and/or obtain adesired conversion of monomer. In some embodiments, the polymerizationor oligomerization reaction time ranges from 1 minute to 5 hours;alternatively, ranges from 5 minutes to 2.5 hours; alternatively, rangesfrom 10 minutes to 2 hours; or alternatively, ranges from 1 minute to1.5 hours.

In an embodiment, the oligomerization produces alpha olefins having atleast four carbon atoms. In further embodiments, the oligomerization toproduce alpha olefins having at least four carbon atoms can becharacterized by a single pass conversion of ethylene of at least about35 weight percent; alternatively, at least 45 percent; alternatively, atleast 50 percent; alternatively, at least 55 percent; alternatively, atleast 60 percent.

In an aspect, the oligomerization process utilizing the α-diimine metalcomplex can produce alpha olefins. In some embodiments, the productcomprises linear alpha olefin having at least 4 carbon atoms. Generally,the oligomerization process producing alpha olefins having at least fourcarbon atoms produces a distribution of several alpha olefins that canbe described by a Schulz-Flory chain growth factor K, where K is definedby the equation:K=X _(q+2) /X _(n)wherein X_(q+2) is the number of moles of alpha olefin produced havingq+2 carbon atoms and X_(q) is the number of moles of alpha olefinproduced having n carbon atoms (i.e. the moles of the preceding alphaolefin produced). In some embodiments, the alpha olefin productdistribution can be described as having a Schulz-Flory chain growthfactor K less than 0.95; alternatively, less than 0.9; alternatively,less than 0.9; or alternatively, less than 0.80. In other embodiments,the alpha olefin product distribution can be described as having aSchulz-Flory chain growth factor K range from 0.4 to 0.95;alternatively, from 0.45 to 0.9; alternatively, from 0.5 to 0.85; oralternatively, from 0.55 to 0.8. Generally, the Schulz-Flory growthfactor can be measured using the number of moles alpha olefins of anytwo adjacent produced alpha olefins. One skilled in the art willrecognize that the measured Schulz-Flory growth factor may not beexactly the same using the number of moles of alpha olefin produced forevery possible adjacent pair of produced alpha olefins. Thus, in someembodiments, the Schulz-Flory growth factor can be an average of two ormore adjacent pairs of produced alpha olefins.

In another aspect, the oligomerization process can produce an alphaolefin product with high selectivity to linear alpha olefins. In someembodiments, the oligomerization process produces a reactor effluentwherein the oligomerized product having 6 carbon atoms has a 1-hexenecontent of greater than 99.0 weight %; alternatively, greater than 99.25weight %; alternatively, greater than 99.5 weight %; or alternatively,greater than 99.75 weight %. In other embodiments, the oligomerizationprocess produces a reactor effluent wherein the oligomerized producthaving 8 carbon atoms a 1-octene content of greater than 98.0 weight %;alternatively, greater than 98.5 weight %; alternatively, greater than99.0 weight %; or alternatively, greater than 99.5 weight %. In yetother embodiments, the oligomerization process produces a reactoreffluent wherein the oligomerized product having 10 carbon atoms a1-decene content of greater than 97.0 weight %; alternatively, greaterthan 97.5 weight %; alternatively, greater than 98.0 weight %;alternatively, greater than 98.5 weight %; or alternatively, greaterthan 99.0 weight %. In yet other embodiments, the oligomerizationprocess produces a reactor effluent wherein the oligomerized producthaving 6 carbon atoms comprises any weight percent 1-hexene as describedherein, the oligomerized product having 8 carbon atoms comprises anyweight percent 1-octene as described herein, and the oligomerizedproduct having 10 carbon atoms comprises any weight percent 1-decene asdescribed herein. For example, in embodiments, the oligomerizationprocess produces a reactor effluent wherein the oligomerized producthaving 6 carbon atoms comprises greater than 99.0 weight percent1-hexene, the oligomerized product having 8 carbon atoms comprisesgreater than 99.0 weight percent 1-octene, and the oligomerized producthaving 10 carbon atoms comprises greater than 99 weight percent1-decene.

EXAMPLES

The data and descriptions provided in the following examples are givento show particular embodiments of the catalysts and methods disclosed,and to demonstrate a number of the practices and advantages thereof. Theexamples are given as a more detailed demonstration of some of theembodiments described above, and are not intended to limit thespecification or the claims to follow in any manner. Table 8 providesthe Structures of the compounds and metal complexes of examples 1-9.TABLE 8 Compounds of Examples 1-9

Example 1 Synthesis of α-Acylimine Compound I((2E)-2-[(2,6-diisopropylphenyl)imino]acenaphthylen-1(2H)-one)

An ethanol (65 mL) solution of acenaphthenequinone (2.00 g, 11.0 mmol)was treated with 1 mL of formic acid, followed by slow, dropwiseaddition (over approx. 8 hrs) of a solution of 2,6-diisopropylaniline(1.56 mL, 8.22 mmol) in 65 mL of ethanol. The resulting mixture wasstirred at 60° C. overnight, cooled and filtered to remove unreactedacenaphthenequinone. After removal of solvent under vacuum, theresulting orange solid was dissolved in ether, filtered and cooled to−10° C. overnight. The orange solid that deposited was filtered, washedwith cold ether and dried. The filtrate was again cooled to −10° C.overnight and additional orange solid was isolated, giving a total yieldof 1.91 g (68.5%). Characterized by ¹H NMR (400 MHz, CDCl₃): 0.88 d, 6H;1.15, d, 6H; 2.82, m, 2H; 8.18, t, 1H; 7.99, d, 1H; 7.81, t, 1H; 7.39,t, 1H; 6.62, d, 1H. (3H's are obscured by the CDCl₃ peak). ¹H NMR (400MHz, MeCN-d₃): 0.89 d, 6H; 1.10, d, 6H; 2.79, m, 2H; 8.27, d, 1H; 8.12,m, 2H; 7.87, t, 1H; 7.45, t, 1H; 7.30, m, 3H; 6.60, d, 1H.

Example 2 Synthesis of α-Acylimine Compound II((2E)-2-[(2,5-di-t-butylphenyl)imino]acenaphthylen-1(2H)-one)

An ethanol (65 mL) solution of acenaphthenequinone (2.00 g, 11.0 mmol)was treated with 1 mL of formic acid, followed by slow, dropwiseaddition (over approx. 8 hrs) of a solution of 2,5-di-t-buytlaniline(1.69 g, 8.25 mmol) in 65 mL of ethanol. The resulting mixture wasstirred at 60° C. overnight, cooled and filtered to remove unreactedacenaphthenequinone. After removal of solvent under vacuum, theresulting orange solid was dissolved in ether, filtered and cooled to−10° C. overnight. The orange solid that deposited was filtered, washedwith cold ether and dried. The filtrate was again cooled to −10° C.overnight and more orange solid was isolated, giving a total yield of2.13 g (70%). Characterized by ¹H NMR (400 MHz, CDCl₃): 1.24, s, 9H;1.31, s, 9H; 6.80, d, 1H; 7.23, d, 1H (resonance partially covered byCDCl₃ peak); 7.40, t, 1H; 7.44, d, 1H; 7.81, t, 1H; 7.97, d, 1H; 8.17,d, 2H.

Example 3 Synthesis of the α-Diimine Metal Complex Having Structure I

A solution containing 0.10 mL (1.0 mmol) of 2-aminomethylpyridine in 50mL of anhydrous butanol was added via cannula to 0.285 g (1.0 mmol) ofα-acylimine compound III and 0.127 g (1.0 mmol) of anhydrous FeCl₂. Theinitially orange solution turned dark brown within 5 minutes anddeposited a dark green solid after stirring overnight under argon at 55°C. The solid was filtered, washed with 6 mL of THF, and dried to yield0.242 g (60%) of dark green product.

Example 4 Synthesis of the α-Diimine Metal Complex Having Structure II

A solution containing 0.10 mL (1.0 mmol) of 2-aminomethylpyridine in 50mL of anhydrous butanol was added via cannula to 0.342 g (0.91 mmol) ofα-acylimine compound I and 0.127 g (1.0 mmol) of anhydrous FeCl₂. Theinitially orange solution turned dark green within 20 min and depositeda dark green solid after stirring overnight under argon at 55° C. Thesolid was filtered, washed with 6 mL of THF, and dried to yield 0.449 g(80%) of dark green product.

Example 5 Synthesis of the α-Diimine Metal Complex Having Structure III

A solution of 0.297 g (1.3 mmol) of 2-(diphenylphosphino)ethylamine in40 mL of anhydrous butanol was added via cannula to 0.440 g (1.30 mmol)of α-acylimine compound I and 0.164 g (1.3 mmol) of anhydrous FeCl₂. Thesolution was stirred overnight under argon at 55° C. The solid thatformed was filtered, washed with a small amount of THF, and dried togive 0.505 g (58%) of dark green product. Recrystallization fromacetonitrile yielded x-ray quality crystals. The obtained crystals weresubjected to x-ray crystallography. An ORTEP diagram for the crystalsproduced in this example is shown in FIG. 1. Selected bond distance andbond angle for catalyst BMS-114 include: Fe—Cl1—2.286; Fe—Cl2—2.313;Fe—N1—2.181; Fe—N2—2.166; Fe—P1—2.497; P1-Fe—N2—135.19;P1-Fe—Cl1—100.77; N2-Fe—Cl1—93.70; N1-Fe—Cl1—156.18; Cl1-Fe—Cl2—111.98.

Example 6 Synthesis of the α-Diimine Metal Complex Having Structure IV

A solution of 0.211 g (0.92 mmol) of 2-(diphenylphosphino)ethylamine in40 mL of anhydrous butanol was added via cannula to 0.263 g (0.92 mmol)of α-acylimine compound III and 0.117 g (0.92 mmol) of anhydrous FeCl₂.The solution was stirred overnight under argon at 55° C. The solid thatformed was filtered, washed with a small amount of THF, and dried togive 0.380 g (66%) of dark green product.

Example 7 Synthesis of the α-Diimine Metal Complex Having Structure V

A 0.202 g sample of 2-aminoethyl(4-chlorophenyl) sulfide (0.93 mmol, 80%pure) was purged with argon for 20 min and then added by cannula to 40mL of anhydrous butanol. This solution was transferred by cannula to0.265 g (0.93 mmol) of α-acylimine compound III and 0.118 g (0.93 mmol)of anhydrous FeCl₂. The resulting solution was stirred for two daysunder argon at 55° C. The dark solid that formed was filtered, washedwith a small amount of THF, and dried to give 0.203 g (39%) of greenproduct. Recrystallization from acetonitrile gave long, rod-likecrystals. The obtained crystals were subjected to x-ray crystallography.An ORTEP diagram for the crystal produced in this example is shown inFIG. 2. Selected bond distance and bond angle for the crystals include:Fe(1)−N(1)=2.132 A; Fe(1)−N(2)=2.197 A. The X-ray crystal structure forthe material and the ethylene oligomerization example provided in Table9 indicate that it is not required that the metal complexing group ofthe α-diimine metal complex for a dative (complexing) bond with themetal atom to have an active ethylene oligomerization catalyst when theα-diimine metal complex is contacted with ethylene and a cocatalyst.Additionally, the X-ray crystal structure indicates that the α-diiminemetal complexes may be isolated in a dimeric form (having bridginghalogen atoms) and have an active ethylene oligomerization catalyst whenthe α-diimine metal complex is contacted with ethylene and a cocatalyst.

Example 8 Synthesis of the α-Diimine Metal Complex Having Structure VI

A solution of 0.235 g (1.02 mmol) of 2-(diphenylphosphino)ethylamine in40 mL of anhydrous butanol was added via cannula to 0.377 g (1.02 mmol)of α-acylimine compound II and 0.130 g (1.02 mmol) of anhydrous FeCl₂.The solution was stirred overnight under argon at 55° C. The resultingdark green solution was reduced in volume to 5 mL in vacuo, depositing agreen solid. This solid was filtered, washed with diethyl ether anddried to give 0.352 g (49%) of green product. Recrystallization was donein MeCN.

Example 9

Polymerization procedure: In separate runs, each of the complexes listedin Table 9 (prepared as a standard solution in methylene chloride, or asa homogeneous mixture in biphenyl) was placed in an NMR tube in asubstantially oxygen- and moisture-free environment. If the biphenylmixture was used, about 0.5 ml of methylene chloride was added to thetube. The NMR tube was then sealed and affixed (using copper wire) tothe internal stirring mechanism of a 500 ml stainless steel autoclave,such that the beginning of stirring would break the NMR tube and releasethe contents into the reactor. The reactor was then evacuated andcharged with anhydrous solvent that contained the aluminum cocatalystThe reactor was then pressurized with ethylene, and stirring wascommenced to initiate the reaction. Ethylene pressure was held constantand reaction temperature was controlled at the temperature set point byinternal cooling coils. Each reaction was commenced at about 30° C.; forselected reactions a maximum exotherm is shown in Table 9. At the end ofeach reaction, the ethylene was slowly vented, and the products wereanalyzed by gas chromatography using the solvent as the internalstandard. The Schulz-Flory constant K was used to estimate the totalamount of product made. TABLE 9 Ethylene Polymerization Results K valueCatalyst Amt Cocat- P_(ethylene) Solvent Length T T_(max) YieldProductivity (C₁₂/ C₆ % C₈ % C₁₀ % Entry Structure (mg) alyst. Al:Fe(psig) (ml) (min) (C.) (C.) (g) (lb/lb cat) C₁₀) purity purity purity 1II 6.0 MMAO 500 400 Heptane, 100 60 55 56 50 8,300 ˜0.5 99.1 98.8 98.6 2VII 4.0 MMAO 500 400 Heptane, 100 30 30 NA 3 VIII 4.0 MMAO 500 400Heptane, 100 30 30 NA 4 III 4.0 MMAO 500 400 Heptane, 100 10 55 57 4311,000 0.61 99.15 98.92 98.75 5 III 4.0 MMAO 500 400 Heptane, 100 30 5562 69 17,000 0.60 99.17 98.92 98.85 6 III 1.0 MMAO 1000 400 Heptane, 10030 40 42 31 31,000 0.60 99.60 99.26 99.25 7 IX 4.0 MMAO 500 400 Heptane,100 10 30 NA 8 X 4.0 MMAO 500 400 Heptane, 100 30 30 NA 9 XI 4.0 MMAO500 400 Heptane, 100 30 30 <5 10 XII 4.0 MMAO 500 400 Heptane, 100 30 30NA 11 I 6.0 MMAO 500 400 Heptane, 100 30 30 <5 12 IV 4.0 MMAO 500 400Heptane, 100 30 55 61 90 22,000 0.42 99.16 98.62 97.97 13 V 4.0 MMAO 500400 Heptane, 100 30 50 52 31 7,700 0.64 98.95 97.43 14 VI 4.0 MMAO 500650 Heptane, 200 30 45 45 15 7300 PE 15 III 2.0 MMAO 500 400 Heptane,200 30 55 57 153 76,000 ˜0.6 16 III 1.0 MMAO 1000 400 Heptane, 200 60 5054 83 83,000 0.60 99.86 99.88 99.36 17 XIII 4.0 MMAO 500 400 Heptane,200 60 40 46 21 5,400 0.61 98.62 98.70 97.54 18 III 0.8 MMAO 1000 800Heptane, 200 30 50 71 94 117,000 0.59 99.70 99.63 99.04 20 III 1.0 MMAO1000 400 Heptane, 200 60 50 71 85 85,000 0.61 99.82 99.81 99.39 21 III0.4 MMAO 2000 800 Heptane, 200 60 40 43 16 40,000 0.54 99.52 99.06 22XIV 4.0 MMAO 500 650 Heptane, 200 60 40 42 30 7,400 0.49 99.20 98.5497.67 23 XV 4.0 MMAO 500 650 Heptane, 200 30 35 37 6.4 1,600 0.60 nd ndnd 24 XVI 4.0 MMAO 500 400 Heptane, 100 20 30 NA 25 IV 2.0 MMAO 1000 400Heptane, 100 30 50 51 45 22,500 0.45 97.93 97.57 97.68 26 XVII 4.0 MMAO500 400 Heptane, 100 15 30 NA 27 XVIII 4.0 MMAO 500 400 Heptane, 100 2530 NA 28 XIX 4.0 MMAO 500 400 Heptane, 100 30 30 NA 29 XX 4.0 MMAO 500400 Heptane, 100 20 30 NA 30 XXI 4.0 MMAO 500 650 Heptane, 200 30 35 354.8 1200 ˜0.6 87.3 31 XXII 8.0 MMAO 500 650 Heptane, 400 60 35 37 NA

While preferred embodiments of the invention have been shown anddescribed, modifications thereof can be made by one skilled in the artwithout departing from the spirit and teachings of the invention. Theembodiments described herein are exemplary only, and are not intended tobe limiting. Many variations and modifications of the inventiondisclosed herein are possible and are within the scope of the invention.Where numerical ranges or limitations are expressly stated, such expressranges or limitations should be understood to include iterative rangesor limitations of like magnitude falling within the expressly statedranges or limitations (e.g., from about 1 to about 10 includes, 2, 3, 4,etc.; greater than 0.10 includes 0.11, 0.12, 0.13, etc.). Use of theterm “optionally” with respect to any element of a claim is intended tomean that the subject element is required, or alternatively, is notrequired. Both alternatives are intended to be within the scope of theclaim. Use of broader terms such as comprises, includes, having, etc.should be understood to provide support for narrower terms such asconsisting of, consisting essentially of, comprised substantially of,etc.

Accordingly, the scope of protection is not limited by the descriptionset out above but is only limited by the claims which follow, that scopeincluding all equivalents of the subject matter of the claims. Each andevery claim is incorporated into the specification as an embodiment ofthe present invention. Thus, the claims are a further description andare an addition to the preferred embodiments of the present invention.The discussion of a reference in the Description of Related Art is notan admission that it is prior art to the present invention, especiallyany reference that may have a publication date after the priority dateof this application. The disclosures of all patents, patentapplications, and publications cited herein are hereby incorporated byreference, to the extent that they provide exemplary, procedural orother details supplementary to those set forth herein.

1. A method for producing an α-diimine metal complex comprising formingat least one imine bond in the presence of a metal salt, metal complex,or combinations thereof.
 2. The method of claim 1, wherein the methodcomprises: a) contacting an α-acylimine compound, a metal salt, and aprimary amine; and b) recovering the α-diimine metal complex.
 3. Themethod of claim 2, wherein: 1) the α-acylimine compound comprises anα-acylimine group and an α-acylimine nitrogen group consisting of anorganyl group consisting of inert functional groups or a hydrocarbylgroup; and 2) the primary amine comprises an —NH₂ group, a metal saltcomplexing group and a linking group linking the metal salt complexinggroup to the —NH₂ group.
 4. The method of claim 3, wherein the metalsalt comprises chromium, iron, cobalt, or mixtures thereof.
 5. Themethod of claim 3, wherein the 1) the α-acylimine group of theα-acylimine compound is derived from an aromatic α-dione and theα-acylimine nitrogen group of the α-acylimine compound consists of a C₁to C₃₀ hydrocarbyl group; and 2) the metal salt complexing group of theprimary amine comprises a dialkyl aminyl group, a diphenyl aminyl group,a dialkyl phosphinyl group, a diphenyl phosphinyl group, an alkyletheryl group, a phenyl etheryl group, an alkyl sulfidyl group, a phenylsulfidyl group, a furanyl group, a thiophenyl group, a tetrahydrofuranylgroup, a thiophanyl group, a pyridinyl group, a morphilinyl group, apyranyl group, a tetrahydropyranyl group, a quinolinyl group, a pyrrolylgroup, a pyrrolidinyl group, or a piperidinyl group and the linkinggroup of the primary amine comprises a C₁ to C₁₀ hydrocarbyl group. 6.The method of claim 3, wherein the 1) the α-acylimine group of theα-acylimine compound is derived from acenaphthenequinone,phenanthrenequinone, or pyrenequinone and the α-acylimine nitrogen groupof the α-acylimine compound consists of a C₆ to C₃₀ aromatic hydrocarbylgroup; and 2) the metal salt complexing group of the primary aminecomprises a dialkyl aminyl group, a diphenyl aminyl group, a dialkylphosphinyl group, a diphenyl phosphinyl group, an alkyl etheryl group, aphenyl etheryl group, an alkyl sulfidyl group, a phenyl sulfidyl group,a pyridinyl group, or a morphilinyl group, and the linking group of theprimary amine is —(CH₂)_(m)— where m ranges from 1-5.
 7. The method ofclaim 3, wherein the 1) the α-acylimine group of the α-acyliminecompound is derived from acenaphthenequinone and the α-acyliminenitrogen group of the α-acylimine compound consists of a2,6-disubstituted phenyl group; and 2) the metal salt complexing groupof the primary amine comprises a diphenyl aminyl group, a substituteddiphenyl aminyl group, a diphenyl phosphinyl group, a substituteddiphenyl phosphinyl group, a phenyl sulfidyl group, a substituted phenylsulfidyl group, a pyridinyl group, or a substituted pyridinyl group, andthe linking group of the primary amine is —(CH₂)_(m)— where m rangesfrom 1-3.
 8. The method of claim 2, wherein the α-acylimine compound isprepared by: a) contacting an α-diacyl compound and a primary amineconsisting of an —NH₂ group and an organyl group consisting of inertfunctional groups or a hydrocarbyl group; and b) recovering theα-acylimine compound.
 9. The method of claim 2, wherein: 1) theα-acylimine compound comprises an α-acylimine group and an α-acyliminenitrogen group consisting of an of an organyl group consisting of inertfunctional groups or a hydrocarbyl group; and 2) the primary amineconsists of an —NH₂ group and an organyl group consisting of inertfunctional groups or a hydrocarbyl group.
 10. The method of claim 2,wherein: 1) the α-acylimine compound comprises an α-acylimine group andan α-acylimine nitrogen group comprising a metal salt complexing groupand a linking group linking the metal salt complexing group to theα-acylimine nitrogen atom; and 2) the primary amine consists of an —NH₂group and an organyl group consisting of inert functional groups or ahydrocarbyl group.
 11. The method of claim 1, wherein the methodcomprises: a) contacting an α-acylimine metal complex and a primaryamine; and b) recovering the α-diimine metal complex.
 12. The method ofclaim 11, wherein: 1) the α-acylimine metal complex comprises a complexbetween a metal salt and an α-acylimine compound comprising anα-acylimine group and an α-acylimine nitrogen group consisting of anorganyl group consisting of inert functional groups or a hydrocarbylgroup; and 2) the primary amine comprises a —NH₂ group, a metal saltcomplexing group, and a linking group linking the metal salt complexinggroup to the —NH₂ group.
 13. The method of claim 12, wherein the metalsalt comprises chromium, iron, cobalt, or mixtures thereof.
 14. Themethod of claim 12, wherein the 1) the α-acylimine group of theα-acylimine compound in the α-acylimine metal complex is derived from anaromatic α-dione and the α-acylimine nitrogen group of the α-acyliminecompound in the α-acylimine metal complex consists of a C₁ to C₃₀hydrocarbyl group; and 2) the metal salt complexing group of the primaryamine comprises a dialkyl aminyl group, a diphenyl aminyl group, adialkyl phosphinyl group, a diphenyl phosphinyl group, an alkyl etherylgroup, a phenyl etheryl group, an alkyl sulfidyl group, a phenylsulfidyl group, a furanyl group, a thiophenyl group, a tetrahydrofuranylgroup, a thiophanyl group, a pyridinyl group, a morphilinyl group, apyranyl group, a tetrahydropyranyl group, a quinolinyl group, a pyrrolylgroup, a pyrrolidinyl group, or a piperidinyl group and the linkinggroup of the primary amine comprises a C₁ to C₁₀ hydrocarbyl group. 15.The method of claim 12, wherein the 1) the α-acylimine group of theα-acylimine compound in the α-acylimine metal complex is derived fromacenaphthenequinone, phenanthrenequinone, or pyrenequinone and theα-acylimine nitrogen group of the α-acylimine compound in theα-acylimine metal complex consists of a C₆ to C₃₀ aromatic hydrocarbylgroup; and 2) the metal salt complexing group of the primary aminecomprises a dialkyl aminyl group, a diphenyl aminyl group, a dialkylphosphinyl group, a diphenyl phosphinyl group, an alkyl etheryl group, aphenyl etheryl group, an alkyl sulfidyl group, a phenyl sulfidyl group,a pyridinyl group, or a morphilinyl group, and the linking group of theprimary amine is —(CH₂)_(m)— where m ranges from 1-5.
 16. The method ofclaim 12, wherein the 1) the α-acylimine group of the α-acyliminecompound in the α-acylimine metal complex is derived fromacenaphthenequinone and the α-acylimine nitrogen group of theα-acylimine compound in the α-acylimine metal complex consists of a2,6-disubstituted phenyl group; and 2) the metal salt complexing groupof the primary amine comprises a diphenyl aminyl group, a substituteddiphenyl aminyl group, a diphenyl phosphinyl group, a substituteddiphenyl phosphinyl group, a phenyl sulfidyl group, a substituted phenylsulfidyl group, a pyridinyl group, or a substituted pyridinyl group, andthe linking group of the primary amine is —(CH₂)_(m)— where m rangesfrom 1-3.
 17. The method of claim 12, wherein the α-acylimine metalcomplex is prepared by: a) contacting an α-diacyl compound and a primaryamine consisting of an —NH₂ group and an organyl group consisting ofinert functional groups or a hydrocarbyl group; b) recovering theα-acylimine compound; c) contacting the α-acylimine compound with ametal salt; and d) recovering the α-acylimine metal complex.
 18. Themethod of claim 12, wherein the α-acylimine metal complex is preparedby: a) contacting an α-diacyl compound, a metal salt, and a primaryamine consisting of an —NH₂ group and an organyl group consisting ofinert functional groups or a hydrocarbyl group; and b) recovering theα-acylimine metal complex.
 19. The method of claim 11, wherein: 1) theα-acylimine metal complex comprises a complex between a metal salt andan α-acylimine compound comprising an α-acylimine group and anα-acylimine nitrogen group consisting of an organyl group consisting ofinert functional groups or a hydrocarbyl group; and 2) the primary amineconsists of an —NH₂ group and an organyl group consisting of inertfunctional groups or a hydrocarbyl group.
 20. The method of claim 11,wherein: 1) the α-acylimine metal complex comprises a complex between ametal salt and an α-acylimine compound comprising an α-acylimine groupand an α-acylimine nitrogen group comprising a metal salt complexinggroup and a linking group linking the metal salt complexing group to theα-acylimine nitrogen atom; and 2) a primary amine consisting of an —NH₂group and an organyl group consisting of inert functional groups or ahydrocarbyl group.